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OBJECT OF THE INVENTION
[0001] This invention refers to a multi-flow dosage cap which contains two “U”-shaped channelled tracks with different radius and a partition with a slit which ends in two holes aligned with the aforementioned pouring tracks.
[0002] The invention develops a dosage cap for pouring liquids, more specifically for pouring viscous liquids and, more particularly, for pouring oils.
BACKGROUND AND SUMMARY OF THE INVENTION
[0003] The use of oil bottles or other recipients containing oil for dressing salads and the like is a common operation, which is widely known in the current state of the art. The recipients used for these purposes incorporate some kind of outlet conduit which generally consists of a hole of reduced diameter allowing the user to control as far as possible the amount of oil poured during the salad dressing operation. Oil bottles have some practical disadvantages, for example the fact that the outlet conduit has a reduced diameter and hence a very limited flow rate. An oil bottle or dispenser is practical when it is used to dress an individual salad or the like, which requires a relatively small amount of oil, but is not so practical when in comes to dressing salads intended for a number of people, in which case the limited flow rate requires a greater amount of handling and time; another drawback consists of the fact that the single outlet with a limited flow rate means that the air drawn into the recipient as the product is extracted also has to circulate through the same conduit as the oil being poured; this shakes the pouring intermittent, with continuous interruptions which hamper the extraction operation by causing the oil to come out in spurts.
[0004] The state of the art shows different valves or rotating mechanisms to modify the pouring flow rate. However, these devices have the disadvantage that the number of parts required for manufacture increases, with the subsequent cost and, on the other hand, residues of the liquids, in particular when viscous liquids are poured, accumulate in the joins, and may compromise the quality of the stored liquid.
[0005] The problem solved by the invention is to find a multi-flow dosage cap with the minimum number of parts, which produces a uniform flow of the liquid.
[0006] The solution found by the inventors is a cap with a lower part with the means to adapt it to the recipient, a pouring channel and an upper part which comprises pouring means. The pouring means are two “U”-shaped channelled tracks with different radii. The channelled tracks are located at diametrically opposed points. The lower part and the upper part of the cap are separated by a partition. The partition contains a slit which ends in two holes with different areas, and the aforementioned channelled tracks are aligned with the holes, i.e. the track with the larger radius is aligned with the hole with the larger area.
[0007] The cap produces two different flow rates of oil. This allows the user to choose which of the two holes should be used at each moment, depending or whether, for example, the salad to be dressed is individual or is a larger salad intended for consumption by more than one person. This cap construction also has the feature that the flow of oil provided is continuous, without interruptions, given that, because only one of the conduits for the oil is used at any one time, the other conduit acts as an air inlet, thus facilitating the extraction of oil.
[0008] The present multi-flow dosage cap has the advantage of being perfectly adjustable to the necks of the current recipients. In a preferred embodiment, the adjustment involves a screw thread or by pressure.
[0009] According to the invention, the design of the presently proposed cap allows various forms of embodiment. In a first embodiment, the interior space of the cap is divided by means of an internal central partition, with a slit in the central partition and two holes. The pouring channel ends in two “U”-shaped pipes or conduits, with different radii, and the pouring conduits are aligned with the holes in the central partition. This means that, by tilting the bottle to one side or another, the desired outlet conduit can be selected, and thus the volume of oil in the chosen flow. The slit allows air to enter and gives a continuous flow.
[0010] In other embodiments of the inventive cap, the internal division may contain an integrated partition running lengthways to the centre of the cap, which determines at the outlet end two conduits or pipes with very different respective flow capacities; one or other of the outlets is selected as described above, i.e. by tilting the bottle to one side or the other. In a preferential embodiment, the central partition is sloping. In addition to the formation of a sloping internal partition, the profile of the partition may either be straight or curved, arched.
[0011] In another particular mode, the cap contains a skirt ring which projects outwards in a radial direction, and is adapted to be coupled to the edge of the neck or the recipient. The skirt prevents any dripping liquid from staining the table.
[0012] The cap may be manufactured with any material compatible with the liquid to be poured. In a preferred mode, it is made of polypropylene and injection-moulded.
[0013] The cap is suitable for the manufacture of oil holders or bottles containing oils.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] FIG. 1 shows representations (a), (b) and (c) corresponding, respectively, to a perspective view, a higher plane view and a cross-section alone the line A-A of the representation (b);
[0015] FIG. 2 shows two representations (a) and (b) corresponding, respectively, to a higher plane view end a cross-section along the line A-A of the representation (a), related to a cap divided internally by a sloping partition with a straight-line profile, and
[0016] FIG. 3 consists of two representations (a) and (b) corresponding to views equivalent to FIG. 2 , but related to a cap divided internally by a sloping partition with a curved profile.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0017] FIG. 1 represents a cap for an oil recipient or the like, indicated in general with the numerical reference 1 , formed of a cylindrical shaped body whose outer surface is interrupted at an intermediate height by a skirt ring 2 , which projects outwards in a radial direction and is adapted to be coupled to the edge of the neck of the recipient. The body, which as stated before is injection-moulded in a plastic material of the polypropylene type, includes an internal partition 3 integrated with the body of the cap, in which there is a slit 4 which extends in a diametrical direction, and at each end of which there are holes 4 a, 4 b of clearly different sizes to allow the passage of flow rates which are also different, depending on the hole 4 a, 4 b chosen on each occasion. The body presents in the upper portion of the cap, i.e. the portion of the cap which, during use, will be outside the neck of the recipient, two “U”-shaped formations 5 a , 5 b with different radius, projecting lengthways, which are set opposite each of the holes 4 a, 4 b , which have a somewhat rounded shape at the end to constitute pouring spouts for the oil extracted from inside the recipient (not shown).
[0018] In this way, tilting the recipient towards the side of one of the pouring spouts provided by the “U”-shaped channels 5 a, 5 b achieves a greater or lesser flow of product, as desired, in continuous fashion with no interruptions of any kind.
[0019] The representations (a) and (b) in FIG. 2 of the drawings show a higher plane view and a cross-section A-A view, respectively, of an alternative embodiment of the multi-flow dosage cap in this invention, which also consists of a body 1 ′ of injection-moulded plastic material, generally cylindrical in shape, with a portion 1 a which has a truncated cone shape in relation to the insertion end of the cap in the neck of the recipient (not represented), which also has a skirt ring 2 projecting outwards in a radial direction at intermediate height, the internal space of which is divided by a sloping partition 6 which takes an ascending direction towards the wall of the cap to form two conduits for the oil, or pipes 6 a, 6 b , with very different capacities and flow rates. Inside, the two pipes have accesses of a approximately equivalent size, while in the direction towards the outside, or outlet direction, the capacity of one of the pipes becomes progressively reduced by virtue of its inclination, by moving closer to the wall of the body 1 ′. This provides two supply capacities which can be selected by the user, simply by tilting the recipient to one side or the other, providing continuous flows with no interruptions of any kind.
[0020] In the representation of FIG. 2 , the internal sloping partition 6 is developed in a straight line. However, as shown by views (a) and (b), respectively, in FIG. 3 of the drawings, the internal space of the cylindrical body 1 ′ of the bi-flow dosage cap in this form of embodiment may be divided by means of a partition 6 ′ which is also sloping but is curved in shape, which starts from an approximately intermediate position in the inside of the cap and, in the direction of the outlet end, approaches the wall of the cylindrical body 1 ′, creating two outlets 6 ′ a and 6 ′ b of appreciably different sizes and outlet flows, delimited by curved walls. The functionality and operation of this form of embodiment is, nevertheless, equivalent to the one provided by the version in FIG. 2 of the drawings. | The invention relates to a multi-flow dispensing stopper containing two U-shaped channels of different radii and a partition with a slit that ends in two openings aligned with said pouring channels. The dispensing stopper is for using in oil bottles. | 1 |
TECHNICAL FIELD
THIS INVENTION relates to a reinforcing strut for overhead sectional doors.
BACKGROUND OF THE INVENTION
Overhead sectional doors can have a number of problems which may be overcome by placing reinforcing struts on the doors. When overhead sectional doors are in the open position, the weight of the door often causes panels of the door to bow downwardly. This is both aesthetically displeasing and can also damage the panels. Placement of struts transverse the panels can reduce the bow in the panels and also prevent the panels from damage.
Most overhead sectional doors are fitted with a remote control operator. This operator is attached to an arm which enables the door to be opened or closed. The arm exerts a pushing or a pulling force on the top of the door section which can be substantially large and may damage the panels of the door. To counter this effect, a strut can be placed at the top edge of the door to cater for these loads.
When a garage door is closed, it becomes a relatively large single surface which has to be able to resist wind pressure. In cyclonic or hurricane winds, the forces that can be generated on the panels are extremely large. The weakest areas on most overhead sectional doors are the top and the bottom edges of the door. Therefore, struts can be placed on the bottom and top edge of the door to counter wind pressure.
Currently, the struts used on overhead sectional doors that are U-shaped in cross-section. The strength of these struts can be dramatically affected by the way in which they are attached to the overhead sectional door. The struts are usually attached by the manufacturer and if not attached correctly, the door may become damaged by the three factors discussed above. Further, the struts that are currently used are quite heavy. The extra weight increases the size requirements of the springs and other components need for the overhead sectional door. This leads to a total cost increase of the overhead sectional doors. Still further, the strength of the current reinforcing struts still permits failure of overhead sectional doors at relatively low loadings.
OBJECT OF THE INVENTION
It is an object of the present invention to provide a reinforcing strut which at least minimises the disadvantages referred to above or provides the consumer a commercial choice.
DISCLOSURE OF THE INVENTION
According to one aspect, the invention provides a reinforcing strut for an overhead sectional door including a pair of oppositely directed feet for fastening the reinforcing strut to the overhead sectional door and a wall extending from an end of each of the feet with the walls in contact with and fixed to one another.
The reinforcing strut may be constructed from a single sheet of material. The material may be a metal such as a steel. The strut may be roll formed.
Any suitable conventional forms of fastening may be employed for the purposes of attaching the feet to the overhead sectional door such as welding, threaded fasteners, adhesives etc.
A lip may extend outwardly from an end of each of the feet. The top of the lip may be turned on itself to produce a dull edge. The lip is usually turned inwardly. The lip may provide additional strength to the reinforcing strut.
The distal edges of the walls may be connected to one another and may be contiguous. Where the edges are connected in this way, an enclosed structure may be formed at that location. Preferably, the enclosed structure is square in cross-sectional shape. A side of the enclosed structure may be at an angle of approximately 135° to that of the walls. A bar may be placed within the enclosed structure to provide additional strength to the reinforcing strut.
The walls may be fixed to one another via various common known fixing means such as welding, threaded fasteners, adhesives etc. Preferably, the walls are fastened to each other through a hole and corresponding folding tab arrangement.
The reinforcing struts may be produced in standard heights. The standard heights may be between 50 mm-100 mm. Preferably, the standard height may be 85 mm.
BRIEF DESCRIPTION OF THE DRAWINGS
A particular preferred embodiment of the invention will now be described with reference to the following drawings in which:
FIG. 1 is a front section view of a reinforcing strut according to an embodiment of the invention.
FIG. 2 is a left side view of a reinforcing strut according to FIG. 1.
FIG. 3 is a right side view of a reinforcing according to FIG. 1.
FIG. 4 is a graph representing strut stiffness comparing known struts with struts of type according to that of the invention.
FIG. 5 is a front section view of a reinforcing strut according to a second embodiment of the present invention.
DETAILED DESCRIPTION OF EMBODIMENTS
The reinforcing strut 10 of FIG. 1 is roll formed from a single sheet of high tensile steel. The length of the steel may be varied to suit various sizes of overhead sectional doors. The thickness of the sheet is 0.55 mm
The reinforcing strut 10 has two feet 11,12 which are used to attach the reinforcing strut 10 to an overhead sectional door. The two feet 11,12 lie in the same plane with the bottom of the two feet 11,12 being substantially flat to aid in the attachment.
A lip is formed at the end of each of the two feet. The two lips 13,14 are substantially perpendicular to the feet. The tops of the two lips 13,14 have been turned inwardly back on to themselves so as to produce a dull edge.
A wall is formed at the opposite end, i.e., the inner ends, of each of the two feet. The two walls 15,16 are substantially perpendicular to the two feet 11,12. A side each of the walls 15,16 abuts against each other for the length of the reinforcing strut 10.
An enclosed structure 17 is formed at the ends of the two walls. The enclosed structure 17 is square in cross-sectional shape. There are two lower 18,19 and two upper sides 20,21 of the enclosed structure. Side 18 and wall 15 are at an angle of 135° with respect to each other. Similarly, side 19 and wall 16 are also at 135° to each other. A bar (not shown) may be placed within the enclosed structure 17 to increase the overall strength of the strut 10.
FIGS. 2 and 3 show left and right side views of the reinforcing strut 10 before the walls 15,16 are fixed together. Trapezoidal holes 22 are punched periodically in wall 15 of the reinforcing strut 10 before roll forming. Similarly, tabs 23 are formed periodically from the right wall 16 of the reinforcing strut 10 before roll forming. Each tab 23 is trapezoid in shape and hinged on its longest side. When the reinforcing strut 10 is roll formed, the tabs 23 become aligned with the holes 22. Each tab 23 is then folded through the hole 22 until its sits flush against wall 15, thus fixing the walls 15,16 together.
FIG. 4 shows a graph representing strut stiffness of a number of different struts. The data obtained was based on a number of tests that were undertaken. Letters A-G represent different struts and their relationship between deflection and load.
Strut A is a U-shaped strut with flanges extending outwardly adjacent the end of the U-shaped section. This strut is currently being used by most manufacturers in the marketplace.
Strut B is a substantially V-shaped strut with flanges connected to ends of the V. It is currently being used in the marketplace but to a lesser extent.
Struts C-F are struts which have the cross-sectional shape of the strut shown in FIG. 1. The wall height of each of the struts is 70 mm, 83.5 mm, 85 mm and 90 mm respectively.
Strut G has the same profile as the strut of FIG. 1. A bar has been inserted into the enclosed structure. The wall height of this strut is 90 mm.
Struts A and B are made of steel sheeting that is 1.0 mm thick. Struts C-G are made of steel sheeting 0.55 mm thick.
The termination of each line on the graph represents the yield point of each of struts. That is, where the strut begins to lose its ability to spring back to its original shape when the load is removed.
STRUTS A-B
Struts A and B were used as a basis for comparison of what is currently available on the market. The results of the testing of these struts is discussed below.
STRUT C
Strut C showed similar strut stiffness to Strut A. However, the yield point of Strut A was considerably higher than the yield point of Strut A. Strut C had a yield point of 210 mm whilst the Strut A had a yield point of only 143 mm.
STRUTS D-F
Struts D-F had a much higher yield than strut B. As height of the strut increased, so did the yield point. Strut B had a yield point of 219 N/m whilst Struts D-F had yield points of 314 N/m, 327 N/m and 363 N/m, respectively. Strut F is considered the maximum height possible without creating problems with aesthetics.
STRUT G
Strut G had by far the largest yield point at 600N meters with a deflection figure of approximately the same as Strut A. It is envisaged that Strut G will be able to be produced for extremely wide doors without a disproportionate increase in weight.
Comparing Struts A and B with Struts F and G, there are a number of advantages which can be established:
(i) Strut F requires 27% less material than Strut A.
(ii) The yield point of Strut F is 165% of Strut A. Therefore, Strut F will be able to cope with 65% greater wind loads.
(iii) Strut G has a yield point 250% of that of Strut A.
(iv) The deflection for Strut F for a given fixed load is 80% of the deflection of Strut A.
(v) The deflection of Strut F for a given fixed load is 48% of the deflection of Strut B.
The lower weight of the reinforcing struts allows smaller springs and other components to be used. Further, fewer struts can also be used to achieve better results. Greater wind loadings can be achieved using the reinforcing struts. Also, wider doors can be manufactured than those currently available because the reinforcing struts can be produced to cope with increased loading. Cost savings may also be achieved.
FIG. 5 is a front section view of a strut 30 according to a second embodiment of the present invention. The strut 30 has two feet 31, 32. A lip 33, 34 is formed at the end of each of the feet 31, 32. The two lips 33, 34 are substantially perpendicular to the feet. The tops of the two lips 33, 34 have been turned inwardly back on to themselves so as to provide a dull edge.
A wall is formed at the opposite end of each of the two feet. The two walls 35, 36 are substantially perpendicular to the two feet 31, 32. The walls abut one another and may be joined to each other in a similar manner to that described in relation to FIGS. 1, 2 and 3.
An enclosed structure 37 is formed at the ends of the two walls 35, 36. The enclosed structure 37 is generally circular in cross section. The second embodiment of FIG. 5 is generally identical to the embodiment of FIG. 1, except that the enclosed structure is generally circular in cross section, as opposed to generally square in cross section. | A reinforcing strut for an overhead sectional door including a pair of oppositely directed feet for fastening the reinforcing strut to the overhead sectional door and a wall extending from an end of each of the feet with the walls overlying one another and fixed to one another. | 4 |
This application is a continuation-in-part of commonly assigned, application U.S. Ser. No. 07/864,890 filed Apr. 2, 1992, U.S. Pat. No. 5,469,199, entitled Wide Inkjet Printhead, incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention pertains generally to inkjet printers and the like and more particularly to printhead data and control circuitry for wide-array printers.
2. Description of the Related Art
Thermal inkjet print cartridges operate by rapidly heating a small volume of ink to cause the ink to vaporize and be ejected through one of a plurality of orifices so as to print a dot of ink on a recording medium, such as a sheet of paper. Typically, the orifices are arranged in one or more linear arrays in a nozzle member. The properly sequenced ejection of ink from each orifice causes characters or other images to be printed upon the recording medium as the printhead is moved relative to the medium. The medium is typically shifted each time the printhead has moved across the medium. The thermal inkjet printer is fast and quiet, as only the ink strikes the recording medium. These printers produce high quality printing and can be made both compact and affordable.
In one prior art design, the inkjet printhead generally includes: (1) ink channels to supply ink from an ink reservoir to each vaporization chamber proximate to an orifice; (2) a metal nozzle member in which the orifices are formed in the required pattern; and (3) a silicon substrate containing a series of thin film resistors, one resistor per vaporization chamber.
To print a single dot of ink, an electrical current from an external power supply is passed through a selected thin film resistor. The resistor is then heated, in turn superheating a thin layer of the adjacent ink within a-vaporization chamber, causing a droplet of ink to be ejected through an associated orifice onto the recording medium.
One prior art print cartridge is disclosed in U.S. Pat. No. 4,500,895 to Buck et al., entitled "Disposable Inkjet Head, " issued Feb. 19, 1985 and assigned to the present assignee.
In a thermal inkjet printhead incorporating these types of discrete printheads, the thin film heaters are selectively energized while a mechanism transports the printhead across a recording medium, typically a sheet of paper. The recording medium is incrementally moved perpendicular to the travel path of the printhead so as to enable printing at virtually any location on the recording medium.
In order to selectively energize the individual thin film heaters, a printhead element is associated with each heater. The printhead element typically consists of a diode or a transistor that can be selectively enabled. Typically, a select line is associated with each printhead element which enables the printhead element when a select signal is received on the select line. In order to minimize the number of select lines, the printhead elements can be arranged in a matrix configuration. In the matrix configuration, the select lines are commonly connected to a plurality of printhead elements, each element having a separate supply line. Thus, a printhead element is selectively enabled by generating a select signal on the appropriate select line and enabling a supply signal on the appropriate supply line. After the printhead element is enabled, a current is produced therein which is passed through the corresponding thin film heater. A typical example of a matrix-type inkjet printer driver is shown in European Patent Application No. 441,635 by Matsumoto et al.
To increase the speed of printing per line on a medium and to reduce the mechanical complexity of a printer, it is known to mount separate printheads side by side to form a fixed array of printheads extending across an entire width of a medium. Selected printing elements across the array of discrete printheads are energized simultaneously to print an entire line of dots onto the medium. After the line is printed, the medium is incrementally shifted perpendicular to the array of printheads, and the printing process is repeated.
Drawbacks to this construction of an array of discrete printheads include increased electrical complexity, difficulty in precisely aligning the printheads with one another, and increasing cost in the providing the plurality of printheads.
As is apparent, with resolutions of inkjet printers becoming greater than 300 dots per inch ("dpi"), alignment of the orifices between discrete inkjet printheads across an array of eight inches or more requires extremely precise positioning to achieve satisfactory spacing between printed dots on a medium. This alignment must be maintained throughout the useful life of the product and under different conditions of duty cycle, temperature, shock, and vibration.
Furthermore, as the resolution increases, the amount of data required to selectively energize the individual thin film heaters grows geometrically. For example, a 300 dpi by 300 dpi printer produces 9000 dots per square inch. In contrast, a 600 dpi by 600 dpi printer produces 36,000 dots per square inch. Thus, doubling the horizontal and vertical resolution quadruples the dot density. In order to selectively energize the corresponding thin film heaters, the rate of the data needed to select the desired thin film heaters must increase in geometric proportion to the increase in the dot density.
In addition, as the resolution increases so does the number of thin film heaters. The size of the integrated driver circuits increases correspondingly. The yield of the silicon devices, however, is inversely proportional to the size of the die. Therefore, as the size of the printhead elements to accommodate the increased number of thin film heaters, the yield of the silicon dies reduces.
Thus, what is needed is a driver design that is flexible in order to accommodate the optimal number of thin film heaters to maximize the yield. Also, what is needed is an improved wide printhead structure which requires a reduced data rate and where precise alignment of the orifices across the printhead may be accomplished simply and precisely maintained over the life or the product and over a wide range of operating conditions.
SUMMARY OF THE INVENTION
It is, therefore, an object of the invention to reduce the data bandwidth requirements of a high-resolution pagewide inkjet printhead interconnect circuitry.
Another object of the invention is to arrange a common printhead element in an array suitable to form a pagewide inkjet printhead.
A further object of the invention is to interconnect the printhead elements in a pagewide array.
A page wide ink jet printhead element is disclosed along with a method of interconnecting a plurality of the elements on a flexible interconnect to form a pagewide inkjet printhead array. The inkjet printhead element comprises a heater array including a plurality of heater elements, each element in communication with an individual ink-jet nozzle. An actuating means is coupled to the heater array for actuating the heater array. The actuating means has a clock input and a fire strobe input for receiving a fire strobe pulse to synchronize the generation of an actuation pulse. The printhead element also includes an address pass-through network or circuitry including an address bus for sending and receiving addresses to and from a previous or upstream element and an address pass-through bus for selectively sending addresses to a subsequent or downstream element. Also, a data pass-through network is included for sending and receiving data to and from the previous and subsequent elements. In addition, the printhead element includes a means for controlling the printhead element coupled to the address pass-through network, the data pass-through network and the actuating means having control input lines for receiving control signals.
A plurality of the printhead elements described above can be arranged on a flexible interconnect circuit having a plurality of interconnect lines connected between the elements. The interconnect lines are used to transmit command and data information to and from the elements in order for the printer controller to specify the desired inkjet nozzles to be actuated. The elements are preferably arranged so that adjacent elements have overlapping nozzles to accommodate thermal expansion in the printhead. The overlapping nozzles can then be selectively enabled to produce the optimal print quality.
An advantage of the invention is that the printhead array hereinafter described can be calibrated to account for variations due to manufacturing or thermal expansion.
The foregoing and other objects, features and advantages of the invention will become more readily apparent from the following detailed description of a preferred embodiment which proceeds with reference to the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective diagram of a 4-color, page-wide printhead according to the invention.
FIG. 2 is a plan view of a portion of one of the printer arrays of FIG. 1.
FIG. 3 is a functional block diagram of electrical control circuitry for the printer of FIG. 1.
FIG. 4 is a first method of interconnecting the printhead elements of one of the arrays of FIG. 1.
FIG. 5 is a second method of interconnecting the printhead elements of one of the arrays of FIG. 1.
FIG. 6 is a plan view of a portion of a flexible interconnect for multilevel interconnection of the printhead elements on the printhead.
FIG. 7 is a plan view of a portion of a flexible interconnect for interconnecting the printhead elements on the printhead which requires only a single level of metallization.
FIG. 8 is a plan view of a portion of a flexible interconnect for interconnecting the printhead elements on the printhead which uses a serial data bus.
FIG. 9 is an enlarged plan view of a portion of a flexible interconnect for a single printhead element showing the chip select lines selectively connected to ground.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 shows a pagewide printhead 10, which includes four separate page-wide printer arrays (12, 14, 16, 18) each dedicated to a separate primary color, e.g., C, Y, M or K. Each of the individual page-wide arrays is designed to span the entire width of a print medium. This arrangement allows the individual page-wide arrays to be fixedly mounted to an ink jet printer frame while the print media is advanced over the top of the individual arrays. The individual arrays are mounted on separate manifolds each of which are in contact with a separate ink reservoir. Each ink reservoir supplies the individual printhead elements (20) of the corresponding array with a constant supply of the appropriate color ink. The mechanical features summarized above are described and shown in detail in U.S. Ser. No. 07/864,890 Filed Apr. 2, 1992, U.S. Pat. No. 5,469,199, incorporated by reference, and so need not be repeated herein.
FIG. 2 shows a portion of array 20 comprising four individual printhead elements 22, 24, 42, 58, as mounted according to FIG. 1. A first printhead element 22 is shown having two rows of nozzles: a top row 26 and a bottom row 28. The top and bottom rows of nozzles 26, 28 each contain four additional nozzles to accommodate an overlapping nozzle pattern, as described below. Individual nozzles of the top and bottom rows 26, 28 are designed to be in contact with the ink supplied by the manifold. Within each of the individual nozzles is a transducer element (not shown) that dissipates energy when a voltage is applied thereto. This dissipation of energy causes the ink to be ejected from the nozzle. The design of the nozzles to eject ink in the aforementioned manner is known in the art to which it pertains and the preferred arrangement is disclosed in U.S. Ser. No. 07/864,890, Filed Apr. 2, 1992, U.S. Pat. No. 5,469,199
In page-wide printers, the horizontal resolution of the printer is determined in large part by the displacement between adjacent nozzles in the same row, i.e., dh. In printheads having only a single row of nozzles, the horizontal displacement is in fact the horizontal resolution of the printer. By having multiple rows, however, the individual rows can be offset from each other so as to create a higher horizontal resolution. In FIG. 2, row 28 is offset from row 26 by precisely one-half dh. This arrangement effectively doubles the horizontal resolution of the printer.
The vertical resolution of the printer is determined both by the vertical displacement dv between adjacent rows as well as the vertical step of the print media over the printhead. By providing multiple rows of nozzles on an individual printhead element the effective vertical resolution can be increased without decreasing the vertical step of the print media. This structure has the effect of decreasing printing time due to the reduced number of steps.
A second printhead element 24 is shown mounted parallel to, and offset from, the first element 22. The spatial relationship between the first printhead element 22 and the second printhead element 24 is replicated across the entire printhead array, such as shown in FIG. 1, to form a first row 56 and a second row 60 of elements. The second printhead element 24 has a top row of nozzles 30 and a bottom row nozzle 32, identical to the first element 22. This allows a single printhead element to be designed and replicated for the entire array. By using a common printhead element, the printhead element can be designed to accommodate the optimal number of heater elements so as to maximize the yield of the elements. The second printhead element 24 is offset from the first printhead element 22 such that two leftmost distal nozzles 34 are opposed to two rightmost distal nozzles 36 of the top row of the first element 22. As a consequence of overlapping said nozzles, the two leftmost distal nozzles 38 of the bottom row of the second element 24 are opposed to two rightmost distal nozzles 40 of the bottom row of the first element 22.
A third printhead element 42 is mounted collinear to first printhead element 22 to form a first row of printhead elements 56. The third printhead element 42 is similarly mounted offset from the second printhead element 24 in a manner similar to the first element 22 except the mirror image. In this case, however, two rightmost distal nozzles 48 are opposed to two leftmost distal nozzles 50 of a top row of nozzles 44 of the third printhead element 42. Once again, as a result of the two rightmost distal nozzles 48 with the two leftmost distal nozzles 50, two rightmost distal nozzles 52 of the bottom row of nozzles 32 of the second element 24 are opposed to two leftmost distal nozzles 54 of a second row of nozzles 46 of the third printhead element 42.
A fourth printhead element 58 is mounted collinear to the second printhead element 24 to form the second row of printhead element 60. The fourth printhead element is offset from the third printhead element 42 in a similar manner as the second printhead element 24 is offset from the first printhead element 22 except the mirror image.
This relationship between adjacent elements, i.e., having overlapping nozzles, is maintained across the entire printhead. Therefore, each printhead element has eight nozzles which overlap with two adjacent printhead elements of the opposite row. Alternatively, the actual number of overlapping nozzles can be modified to accommodate the anticipated amount of thermal expansion or the anticipated placement tolerance of the elements. Such an overlap allows for a simple alignment process from head-to-head in the axis of the printer, and adds 8 nozzles per head. The purpose of overlapping the nozzles will become more clear in the description of the individual elements that follows.
FIG. 3 shows a control circuit 63 of an individual printhead element 22, 24, etc. The control circuitry 63 is included in each of the printhead elements to enable the elements to communicate between themselves and with a printer controller (not shown) which specifies the individual printhead elements. The printhead element has an address bus 64 for receiving addresses, a data bus 66 for receiving data and command information, and control inputs 68 for receiving control signals from adjacent printhead elements. In addition, the printhead element has a system clock input 70 for receiving a clocking signal, and an adjusted system clock output 72 for providing an adjusted system clock output signal. A power input 74 and a ground input 76 are connected to printhead element to provide a power and ground path for the printhead element electronic circuitry. A fire strobe input 78 is provided for receiving a fire pulse to synchronize the firing of the transducer elements. The printhead element also includes an address pass-through bus 80 for connecting to the next serial printhead element in the printhead sequence. Similarly, a data command pass-through bus 82 exists in order to communicate data and command information to the next serial printhead element in the printhead sequence.
The printhead element operates under the control of microsequencer 84 having control logic, which, in the preferred embodiment, is implemented using a programmable logic array, as is known in the art. The microsequencer 84 is coupled to a read-only memory 86 (ROM) or other memory means for storing microsequencer instructions. The read-only memory 86 includes an addressing control bus 88 coupled between the microsequencer 84 and the read only memory 86, as well as a data bus 90. The microsequencer 84 is also coupled to a stack memory 94 having a stack pointer for pointing to the current location in the stack. The microsequencer 84 is coupled to the stack 94 through bus 96. The stack 94 operates in a conventional manner as a temporary storage for the most recent data operands of the microsequencer 84. The stack 94 is further coupled to a random access memory (RAM) 98 over bidirectional bus 100. The random access memory 98, in the preferred embodiment, is a static RAM implementation using conventional CMOS technology. The microsequencer 84 and its associated memory components ROM 86, stack 94, and RAM 98, constitute the core control system of the printhead element. In an alternative embodiment, this system could be replaced by a microprocessor-based control system having similar capability.
The microsequencer 84 and associated memory system accomplishes all of the major control functions within the print element. These functions include calculating extended address functions, the printing of patterns, the determination of the locations to be printed and other associated training functions. The purpose of these functions will become more clear in the detailed description of the operation included below.
Address bus 64 is coupled to an address decode and address storage block 102 where the incoming addresses received on address bus 64 are decoded and stored for subsequent use. The addresses specify which printhead element is affected by the current data transmission. The address pass-through bus 80 is coupled to an address output pass-through block 104. Address pass-through block 104 is designed to facilitate the flow of addresses between adjacent printhead elements in the sequence. The address stored in decode and storage block 102 is coupled to the address pass-through block 104 through internal pass-through bus 106. The internal pass-through address bus 106 allows addresses received on address bus 64 to pass through address pass-through block 104 and onto address pass-through bus 80. Connected in this manner, addresses are allowed to propagate along the printhead array under the control of the individual printhead elements.
Control inputs 68 are coupled to control block 108 which includes control registers for the microsequencer 84, control decode and encode logic, and input/output control. Control block 108 is coupled to microsequencer 84 through control bus 110. Control bus 110 transmits control signals from the microsequencer 84 to the control block 108. The control signals convey information about the current instruction that the microsequencer 84 is executing to allow the control block to produce the appropriate response. The control block 108 includes control points 112 that are coupled to a plurality of the logic blocks in order to control and coordinate their activity, e.g., chip select, read or write.
Data bus 66 is coupled to storage registers and decode logic block 67. Command information is sent and received by storage registers and decode logic block 67 over the data bus 66. The command information specifies the desired operation of the heater elements in array 114, such as "fire" or "blank," for the specific pattern of dots desired. In addition, the data bus 66 receives microcode instructions to be executed by microsequencer 84. The data received on the data bus 66 also includes identification and/or personality information for the overall printing environment. The identification information could be the generated by on-line testing and assembly functions during the manufacture of the printhead or based on the actual printer itself. Additionally, drive pulse patterns can also be input to the printhead element over data bus 66, to permit unique operation at relatively high repetition rates for firing the heater array 114 on demand.
The printhead elements each include a heater array 114, which produces the thermal energy required to eject the ink from the inkjet nozzles, and means for driving the heater array. The means for driving the heater array can include skew adjust storage drive block 92 which adjusts the drive pulse provided to the heater array 114 in order to compensate for system level variations, as described further below. As indicated above, the skew adjust block 92 is coupled to the read-only memory 86 through ROM data bus 90. The skew adjust block receives information from the read-only memory over ROM data bus 90 to indicate the appropriate adjustment required for the current system operating conditions. Skew adjust block 92 is further coupled to random access memory 98 through bidirectional bus 100. The skew adjust block 92 is coupled to driver pulse generator 116 which also includes a multiplexer to final drive circuit 118. The multiplexer selects the appropriate heater element of the heater array 114 for a given set of inputs. The skew adjust block 92, with associated RAM 98, increases print quality and reduces manufacturing requirements by modifying the printing pattern due to variations in the manufacture of the unit.
The driver pulse generator 116 is coupled to the skew adjust block 92 through drive bus 120 and coupled to final drive circuit 118 through final drive bus 122. The drive pulse generator 116 is further coupled to drive pulse shaped storage register 124 through bus 126. The drive pulse shape storage register 124 stores information on the current pulse width of the drive pulse produced by drive pulse generator 116. The drive pulse generator 116 produces a drive pulse signal over final drive bus 122 that is coupled to the final drive circuit 118. The final drive circuit 118 further refines the drive pulse signal to produce a final drive signal on heater bus 128 that is coupled between the final drive circuit 118 and heater array 114. In addition, the driver pulse generator 116 is coupled to power control logic block 130 which receives a system clock signal over system clock input 70 and produces an adjusted system clock signal on adjusted system clock output 72. The power control logic block 130 produces a synchronization signal that is coupled to the pulse drive generator 116 over synchronization line 132.
In the preferred embodiment, a paper velocity and positive analysis circuit 134 is included to receive paper velocity and position information from an external paper velocity and position transducer 136 over transducer lines 137, coupled between paper velocity analysis circuit 134 and the external paper velocity position transducer 136. The paper analysis circuit 134 permits a more accurate understanding of the precise location of the print media and hence improve the print quality once again.
The printhead element may also include a thermal sense circuit including thermal sense analysis circuit 139, thermal sense element 141 and a multiplexer 143. One major issue in thermal inkjet printing is the fact that as the duty cycle of a print-head increases, there can be a considerable increase in the temperature of which can lead to a reduction in print quality. The thermal circuit allows the printhead element to compensate for increases in thermal temperature. The thermal sense element 141 detects the temperature. The thermal sense circuitry 139 can then adjust the rate of data transfer, and/or printing, by modulating the output clock 72, to control the temperature of the heater elements and thereby reduce both the overall peak power demand of the printing unit as well as increase the print quality.
The power control logic block 130 aids in this control of the peak power by adjusting the system and internal clocks to reduce the overall power consumption. In addition, to maintain the power consumption within an appropriate range, the printhead array can reroute printer commands back to the printer processor (not shown) to reduce printing speed if the temperature of the array or a location in the array was exceeding any design specification.
Referring now to FIGS. 4-5, a plurality of individual printhead elements 1-2N are mounted on a flexible interconnect circuit 138 to form a printhead array, such as those shown in FIG. 1. The flexible interconnect circuit is formed on a flexible insulative material having integral conductors. Alternatively, the interconnect could be formed using conventional rigid circuit board material. The individual elements are arranged in a first row of elements 140 and a second row of elements 142. The flexible interconnect circuit 138 provides for the electrical interconnect between all of the individual printhead elements. There are two distinct methods of interconnect as described by the invention. The first interconnect method, shown in FIG. 4, is to serially connect each of the individual elements in the first row 140 from left to right, i.e., 1, 3, . . . 2N-1, and then to each of the elements in the second row 142 from right to left, i.e., 2N, 2N-2, . . . 2. In this way, very little additional area is consumed by the individual conductors connecting between the individual printhead elements.
A second interconnect method is shown in FIG. 5. In this method, the individual printhead elements are alternately serially connected between the first and second rows 140, 142. In this way the conductors connect the elements from left to right in the order shown, i.e., 1, 2, 3, . . . 2N. The benefit of this interconnect method is that the elements are connected in the same order as the nozzles on the printhead. The details of the interconnect methods and the corresponding electrical interconnect are described below.
Referring now to FIG. 6, the back side of the flexible interconnect 138 is shown. A first ink manifold 144 is shown connected to a first row of nozzles by short conduits for supplying ink from the ink manifold 144 to the first row of nozzles 146. Similarly, a second ink manifold 148 is shown coupled to a second row of nozzles by conduit for supplying ink deposited in the second ink manifold 148 to the second row of nozzles 150. The printhead elements are mounted on the opposite side the flexible circuit 138 (see FIGS. 4 and 5) in the area defined by the two rows of nozzles 146 and 148. Each nozzle of the first and second rows are coupled to an output driver of the individual printhead element.
A plurality of conductors 152 is shown coupled to contact pads 154. The printhead driver (not shown) is mounted on the flexible interconnect 138 so that the leads of the printhead driver are in electrical contact with contact pads 154. In this way, address and data information can be transmitted to the individual printhead driver via conductors 152. Conductors 152 are electrically connected to a second level of metallization on a front side of the flexible interconnect 138 through vias 156. Thus, all of the elements on the printhead array receive the same information substantially simultaneously. This implementation is known herein as a parallel bus implementation.
Alternatively, a parallel bus implementation can be implemented on the flexible interconnect with only a single level of metallization as shown in FIG. 7. In the parallel bus implementation shown in FIG. 7, conductors 168 are connected substantially similarly to each of the individual printhead elements on the array. The conductors 168 are routed across the face of each printhead element thereby eliminating the vias that were required in FIG. 6 to connect the second level of metallization. The conductors can be routed on the flexible interconnect 138 as shown or alternatively routed through the printhead element (not shown) by placing the traces on the silicon die of the printhead element. Two separate buses which are required to carry significant currents, the power supply bus 160 and ground bus 162, are routed as separate traces parallel to the row of printhead elements. The individual connections to the power supply bus 160 and the ground bus 162 are provided by separate conductors 164 and 166, respectively. This provides a low impedance path for the current supply to the transducer elements on the printhead elements.
In FIG. 8, a serial bus implementation is shown on a flexible interconnect 168 having a single level of metallization. The serial implementation is a further simplification of the parallel implementation by requiring only a single conductor to transfer information between electrically adjacent elements on the printhead. A serial output contact pad 169 is connected to a serial input contact pad 170 of the electrically adjacent element through first conductor 172. Similarly, a second serial output contact pad 174 is connected to a second serial input contact pad 176 through second conductor 178. By serially connecting the elements in this manner, only a single conductor is required between electrically adjacent elements to communicate address and data information between the two.
Both the parallel and serial implementations require a means for assigning a unique address to each of the elements along the printhead array. In this way, data that is sent out along the bus, whether it be serial or-parallel, is received by the appropriate printhead element. In FIG. 9 a first means for assigning a unique address to the printhead element is shown. A conductor 180 that is connected to the ground bus 162 (FIG. 8) is connected to a ground contact pad 182 as well as one or more chip define pads 184. The precise manner in which conductor 180 is connected to the chip define pads 184 determines the unique address that is assigned to the particular element.
The corresponding printhead driver (not shown) has pullup resistors at the input pads on the printhead elements corresponding to the locations of the chip define pads 184. Thus, if a chip define pad is not connected to ground, the corresponding chip define input, as seen by the printhead element, will be at a logic "1". Alternatively, if the chip define pad is connected to ground, the corresponding chip define input will be at a logic "0". In this manner, the chip define inputs comprise a binary address corresponding to the particular printhead element. In an equivalent embodiment, the chip define pads could be selectively connected to the positive supply voltage V cc and the printhead element have pulled down resistors. The number of chip define pads that are required is a function of the number of printhead elements that comprise the printhead array. The number of chip define pads needed can be determined by the following equation: Number of Pads=LOG 2 (N), where N equals the number of elements in printhead array.
In the preferred embodiment, the chip define pads are connected to grounds so that successive elements on the printhead array have increasingly greater addresses. Once the unique address has been established, the individual printhead elements can compare the address received over the address bus to that programmed on the chip define pads. In the event that the address received on the address bus matches that received on the chip define pads, the printhead elements receives the accompanying data received on the data bus as a command directed to that particular element.
Alternatively, the printhead elements can "learn" their address through a initialization sequence, as described in detail below. In the initialization sequence, the first printhead element receives a first "strobe" from the printer logic to indicate the beginning of the initialization sequence. Since it is the first printhead element in the sequence, it assigns to itself the first address and passes that address on to the next element in the sequence. The next element in the sequence receives this address over the data bus and assigns itself the next address in the sequence and passes this address on to the next element in the sequence. This process continues until all of the elements have been assigned an address. This can be accomplished by having a power up default address that is used for all of the printhead elements before they are assigned an address.
OPERATION
As described in the background of the invention, one of the primary problems with designing high-resolution, pagewidth printheads is the amount of data required to selectively enable the individual heater elements. The present invention minimizes the amount of data necessary to specify the individual heater elements by sending high level print commands to the individual printhead elements. The commands can specify a range of nozzles to be printed, e.g., a vector, or even an entire geometrical object such as a circle. The printhead element control circuitry then interprets the command and actuates the appropriate heater elements. The number of available commands determines the size of the required data bus over which the commands are passed. For example, an 8-bit data bus will support up to 256 unique commands, i.e., 2 8 =256.
In order to calculate the number of address bits required by the address bus, the total number of heater elements is required. For a 4-color, 600 dpi printhead spanning a 12 inch (30.5 cm) wide page, there are approximately 28,800 individual heater elements. Thus, an address bus having 16-bits is more than adequate to individually address each heater element, i.e., 2 16 =65,536. In preferred practice, each printhead element is designed to have 4 extra nozzles at each end for overlap to its two nearest neighbors, as shown in FIG. 2. Therefore, assuming each printhead element normally drives 300 heater elements, the actual number of nozzles which need independent addresses is therefore (300+8 nozzles per head)*(24 heads/array)*4(arrays/printer)=29,568, which is still well within the capacity of a 16-bit address. In order to reduce the number of address lines, however, two 8-bit address portions, i.e., upper and lower bytes, can be transmitted in succession using only an 8-bit address bus.
As mentioned before, there are about 28,800 independent locations on any 1/600" column on a 12 inch (30.5 cm) page. This means that the page-wide array and associated printer will need to go through some kind of learning process to determine how to overlap the array elements. This process need be done only when the array is physically disturbed from its equilibrium position, such as one of the printhead elements are replaced. When the array is first manufactured, or whenever any element is replaced, the print-array shall (with an operator or computer's intervention) perform test prints to determine the selection of the overlapping nozzles as well as the firing order.
Alternatively, the overlapping nozzles can be randomly overlapped in an attempt to diffuse any errors of alignment. The result in the array is that when these "edge-overlap" nozzles are in use, it is likely that the dots will emit from one of 4 nozzles in a gaussian distribution with some pseudo-random sequencing. The result to the eyes of the observer is that it will not be possible to observe the point where one head in the array is printing over and above where the next head is printing. The process of assigning overlapping nozzles can be fully automatic or completely manual, depending upon cost of installation and price of printer.
Once the overlapping nozzles have been assigned, as described above, each printhead element will determine, i.e., learn, which nozzle addresses are associated with the element. This address information is stored in the non-volatile memory within the printer and used whenever a command is issued over the data bus.
The printhead elements teach/learn their proximity to/from adjacent elements. A first element in the array receives a first "strobe" from the printer logic and then passes information on to the remaining elements. Since it is the first chip, it represents the first 1/2 inch (1.27 cm) of print zone, and recognizes that it is both responsible for the page-edge border as well as the next chip overlap. This, in the case of the black printing array, represents the first 300 dot locations on the page.
At this point, it is necessary to realize that the printer will be sending information regarding absolute dot location, while the print array will be "relatively" positioned. The conversion from absolute dot location to relative dot address will be performed by each printhead on the data stream. In other words, the data arrives at the first printhead in the array. That printhead then decodes the data for its relative locations (assuming it has already trained itself and the other elements of the array as to their overlap locations) and then will change the addresses for the remainder of the array prior to forwarding the data to them. It will merely not send data which is solely destined for it. The remainder of the array will behave similarly, i.e., the other elements will modify data as it enters to forward the remaining data elements to their proper destinations. Whenever a new element arrives in the array, only the elements directly upstream and downstream from it will therefore need to re-train themselves to establish the boundaries of the data to receive, since that chip will have a new algorithm for data transfer.
The complexity of the commands sent to the printhead elements determines the complexity required in the control engine of the printhead elements. The more complex the command set, the more "intelligent" the elements must be in order to decode the commands. The more complex the command set, however, the lower the bandwidth required to transmit the commands to the elements.
For example, in a simple embodiment, each nozzle address can be individually addressed. Although a simple printhead element control engine can be used to decode these commands, this places a tremendous bandwidth requirement on both the address and data bus, e.g., 91 MHz data transfer rates. In a more sophisticated embodiment, each printhead element assumes that if a particular nozzle address is not received, no dot is to be printed. For text printing, the usual coverage is on the order of 5 to 10% of the full surface of the paper, and, in addition, text is primarily of one color only. This results in a significant decrease in the bandwidth required, e.g., 7.5 MHz data transfer rates, which is slower than most personal computer bus speeds.
In a yet more intelligent embodiment, logical instructions are used, such as those mentioned above, to specify the operation for a plurality of nozzles in a single command. In this more intelligent array, 8-bit data permits up to 256 separate commands. For the sake of rapid filling of a memory array within the printhead array, however, filling bit-by-bit when a command is to make a line or a colored region is unnecessary. Instead, a command such as "print 1's on every dot location from current address to next address sent" would easily reduce the data transfer rate in graphics mode. The entire series of PCL™ languages by Hewlett Packard of Palo Alto, Calif., are in essence, reductions to practice of this form of data compression.
Having described and illustrated the principles of the invention in a preferred embodiment thereof, it should be apparent that the invention can be modified in arrangement and detail without departing from such principles. I claim all modifications and variation coming within the spirit and scope of the following claims. | A plurality of inkjet printhead elements are arranged to form a pagewide printhead array. The elements are secured to a flexible interconnect to allow for communication between the individual elements and a printer controller. The elements are arranged in the array so that one or more nozzles overlap nozzles of the two adjacent elements. The printer controller specifies the desired drivers of the heater elements to be actuated in commands sent to the first element in the array over the flexible interconnect. The printer elements monitor the interconnect to determine whether the command specifies a heater element under their control. The printer elements then actuate the specified heater element to cause an ink droplet to be ejected from a nozzle corresponding to the selected heater element. | 1 |
BACKGROUND TO THE INVENTION
The invention relates to a clamp, and in particular to a clamp for securing diapers.
Many conventional clamps have opposed jaws which are biased towards one another by a resilient member, such as a spring. Lever arms are usually provided on each jaw to force the jaws apart. The jaws of these clamps are generally biased fairly strongly towards one another, which makes them unsuited to applications such as the fastening of diapers, as they may tend to pinch the baby wearing the diaper if carelessly applied. Furthermore, an outer face of one of the jaws is liable to bear against the infant's skin, which may lead to irritation.
SUMMARY OF THE INVENTION
According to the invention there is provided a clamp comprising a first jaw which includes a first limb, a second opposed limb and an interconnecting bight portion extending between the first and second limbs; a second jaw being mounted pivotably towards the free end of the second limb; locking means for locking the second jaw relative to the first jaw in a plurality of degrees of closure; and release means for releasing the locking means, the first limb terminating in an aperture and the free end of the second jaw being pivotable towards the aperture for urging a portion of material to be clamped between the first and second jaws into the aperture.
Preferably, the locking means comprises a ratchet, a pawl component, and biasing means integral with the pawl component for biasing the pawl component into engagement with the ratchet and allowing unidirectional movement of the second jaw towards the aperture in the first limb.
Conveniently, the ratchet is formed at the pivoted end of the second jaw and the pawl component is carried by the second limb.
In a preferred form of the invention, the release means comprises a finger-engagable tab integral with the pawl component for compressing the biasing means and disengaging the pawl component from the ratchet to allow bidirectional pivotal movement of the second jaw.
Advantageously, the second limb comprises a pair of spaced apart parallel fingers, jaw mounting means being located towards the free ends of the fingers for pivotably mounting the pivoted end of the second jaw between the fingers, and pawl mounting means being located rearwardly of the jaw mounting means for mounting the pawl component pivotably between the fingers.
In a preferred form of the invention the clamp includes a web having a landing surface extending between the pair of fingers, the biasing means on the pawl component being in the form of a rearwardly extending leaf spring which abuts the landing surface, and the release means being arranged above the leaf spring for compressing the leaf spring against the landing surface.
The jaw and pawl mounting means are preferably in the form of respective front and rear pairs of apertures, a pair of front stub axles extend laterally from opposite sides of the pivoted end of the second jaw for pivotal engagement with the front pair of apertures and a pair of rear stub axles extend laterally from opposite sides of the pawl component for pivotal engagement with the rear pair of apertures.
Conveniently, the fingers are elastically deformable, the lower ends of the rear stub axles are chamfered, an axle-receiving channel extends downwardly from an upper edge of each finger along an inner face thereof to each rear aperture, for facilitating the introduction of the stub axles into the rear apertures in a snap fit during assembly of the clamp.
The ratchet and pawl may be recessed or flush relative to a side profile of the second limb.
The free end of the second jaw preferably describes a locus which extends into the aperture, the free end being provided with material-engaging formations for urging a portion of material through the aperture and proud of the outer surface of the first limb for providing a cushioning effect.
In an alternative form of the invention, the pawl component may be formed integrally with the second limb, the pawl component being connected to the second limb by means of a resilient neck which serves as a spring for biasing the pawl component against the ratchet.
The clamp may be formed from three separate unitary components, namely the first jaw, the second jaw and the pawl component.
All the components of the clamp are preferably moulded from a plastics material.
In one common application, the clamp is adapted for use as a diaper clamp for clamping the ends of a diaper together.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a perspective view of a first embodiment of a clamp of the invention in the open position;
FIG. 2 shows a perspective view of the clamp of FIG. 1 in the closed position;
FIG. 3 shows an exploded view of the various components making up the clamp of FIGS. 1 and 2;
FIG. 4 shows a top plan view of the first embodiment of the clamp in the open position;
FIG. 5 shows a cross-sectional side view of the clamp in the open position on the line 5--5 of FIG. 4;
FIG. 5A is a fragmentary enlargement of FIG. 5;
FIG. 6 shows a similar cross-section to that of FIG. 5 with the clamp in the closed position;
FIG. 7 shows a side view of a second embodiment of a clamp of the invention, and
FIG. 8 shows a cross-section on the line 8--8 of FIG. 7.
DESCRIPTION OF EMBODIMENTS
The clamp illustrated in FIGS. 1 to 6 comprises a first C-shaped jaw 10 and a second jaw 12. The first jaw 10 has a first lower ring-shaped limb 14 defining a circular aperture 16. A curved bight portion 18 interconnects the lower ring-shaped limb 14 with a second upper limb 19 comprising a pair of fingers 20 and 22. A sprung pawl component 24 is mounted pivotably between the fingers 20 and 22 on a pair of stub axles 26 and 28 which nest in complemental circular apertures 30 and 32 formed towards the base of the fingers.
The sprung pawl component 24 is provided with an integrally moulded resilient foot which serves as a leaf spring 34. The free end of the leaf spring 34 bears against a web having planar landing surface 36 which extends transversely between the fingers 20 and 22 at the upper end of the bight portion 18. Located just above the leaf spring 34 is a finger-engagable tab 38, the upper surface of which is provided with serrations 40. A tooth 42 projects from the front end of the pawl. The tooth 42 is engagable with an arcuate toothed ratchet arrangement 44 formed at the pivoted end of the second jaw 12. The tooth 42 is biased into engagement with complemental recesses 46 in the toothed ratchet arrangement by virtue of the leaf spring 34 bearing against the landing surface 36. In order to release the tooth 42 from the ratchet arrangement 44, the thumb or finger is pressed downwardly against the serrations 40 on the upper surface of the tab 38, thereby compressing the spring 34 and disengaging the tooth 42 from the recess 46 in the ratchet arrangement 44 so as to allow free bidirectional pivoting of the second jaw 12 relative to the first jaw 14.
The second jaw 12 is provided with a pair of stub axles 50 and 52 which locate in respective circular apertures 54 and 56 defined in circular formations 58 and 60 at the free end of the fingers 20 and 22. The second jaw 12 pivots on the stub axles 50 and 52 between an open position illustrated in FIGS. 1 and 5 and a closed position indicated in FIGS. 2 and 6. The second jaw 12 is essentially of hollow construction, having recesses 62 and 64 divided by a central web 66. The free end of the second jaw 12 terminates in a claw 68, the front face of which is provided with material-engaging serrations 70. With the second jaw 12 in the open position, as is illustrated in FIGS. 1 and 5, the clamp can be clamped over the ends 72 and 74 of a diaper. The second jaw 12 is then pressed downwards to the closed position illustrated in FIGS. 2 and 6, the claw 68 of the second jaw describing a circular arc or locus 76 which has both downward and inward components as is illustrated by arrows 76A and 76B. The claw 68 and the serrations 70 snag the outer surface of the diaper end 72. The diaper ends 72 and 74 are thus drawn both rearwardly towards the bight portion 18 and downwardly through the circular aperture 16. The diaper ends 72 and 74 tuft through the aperture 16, as is illustrated at 75 in FIG. 6. As a result, the infant's skin is spaced apart and cushioned from the outer surface 78 of the first jaw by means of the tufted portion, which stands proud of the outer surface 78. In the normal closed position, no portion of the clamp is therefore actually in contact with the skin of an infant.
The various components of the clamp illustrated in FIGS. 1 to 6, namely the first jaw 10, the second jaw 12 and the pawl component 24 are specially designed for easy and automated assembly. The fingers 20 and 22 are elastically deformable, and can be biased ontwardly. The stub axles 26 and 28 on the pawl 24 have chamfered lowered ends 80. Channels 82 and 84 lead from the upper edges and along the inner faces of the fingers 20 and 22 to the apertures 30 and 32. In order to locate the stub axles 26 and 28 within the apertures 30 and 32, the fingers 20 and 22 are merely splayed slightly apart and the chamfered lower portions 80 of the stub axles 26 and 28 are guided into the channels 82 and 84. The pawl 24 is then pushed downwards, which causes the stub axles 26 and 28 to engage the apertures 30 and 32 in a snap fit. The second jaw 12 is then fitted by merely splaying the fingers 20 and 22 and inserting the stub axles 50 and 52 into the apertures 54 and 56.
Referring now to FIGS. 7 and 8, a second embodiment of a clamp of the invention is shown. A first jaw 86 has the same basic C-shaped configuration as the jaw 10 illustrated in FIGS. 1 to 6. A second jaw 88 is hinged pivotably to the first jaw 86 about an imaginary axis 90. A tongue 92 protrudes from the front portion of the upper limb of the first jaw 86, and extends between a clevis, formed at the rear of the second jaw 88, only one &/rk 94 of which can be seen in FIG. 6. A pawl component 96 is moulded integrally with the first jaw 86, the pawl component having a rearwardly extending finger-actuable tab 98 and a forwardly extending pawl portion 100 having a plurality of saw teeth 102 formed therein. The pawl component 96 is joined to the upper limb of the first jaw 86 by means of a resilient neck 104.
The second jaw 88 has a arcuate ratchet arrangement 106 constituted by a plurality of saw teeth 108. As is clear from the drawing, the saw teeth 102 and 108 mesh complementally with one another. The second jaw 88 is able to pivot in the direction of arrow 110, as the shallow inclined surfaces of the respective saw teeth 102 and 108 are able to glide over one another, to a closed position indicated in broken outline at 111. The second jaw 88 is unable to pivot in the opposite direction as the steep faces of the saw teeth 102 and 108 bear against one another and interlock.
In order to disengage the saw teeth from one another, the tab 98 is depressed downwardly to a position indicated in broken outline at 112, which effectively causes the pawl component 96 to pivot about the neck 104, thereby raising and freeing the saw teeth 102 from the saw teeth 108. This allows the second jaw 88 to pivot back to the open position.
A locking formation 114 may optionally be provided for locking the pawl 96 in the engaged position. The locking formation 114 is constituted by a slot 116 which extends through the upper limb of the first jaw. A C-shaped slide 118 has re-entrant portions 120 which hold the slide 118 captive within the slot 116. The slide 118 is moveable from a locked position to a released position, indicated in broken outline at 122, which allows the tab 98 to be depressed so as to release the ratchet arrangement 106.
The clamp illustrated in the first and second embodiments is formed entirely from a plastics material such as acetal, which is non-toxic and which will not react to urine or faeces. The dye which colours the acetal is likewise non-toxic and non-reactive. Furthermore, the plastics material has a smooth finish 7hich allows it to be cleaned easily. The rounded edges and minimal protrusions reduce the possibility of the baby being injured, as the rounded edges are not able to pierce or scratch the skin of the baby. The ratchet arrangement illustrated in both the first and second embodiments is recessed away from the outer surface of the clamp, thereby reducing the possibility of the teeth of the pawl or ratchet coming into direct contact with the skin of the infant. It is only the smooth, rounded outer edges which contact the infant. As was described earlier on in the specification, the circular aperture in the first jaw accommodates a tufted portion of the diaper which extends beyond the lower outer surface of the clamp and cushions the infant's skin against direct contact with the clamp.
In the closed position indicated in FIGS. 2 and 6, and in broken outline in FIG. 7, the first jaw experiences a moment of force in the direction of arrow 124, which is directed substantially towards the axis of rotation of the first jaw. This force, relative to the ratchet teeth, is radial rather that tangential, 7hich serves to place minimal strain on the ratchet teeth, and thereby allows a less robust and a potentially less harmful ratchet-and-pawl arrangement to be used, in which the teeth and serrations are too small to scratch or irritate the skin of the infant.
Owing to the ratchet and pawl, the degree of closure of the second jaw is variable, thereby providing for different thicknesses of material to be clamped.
The clamp of the invention is not confined to a diaper clamp, but may be used in many applications, for instance as a papaer clip or as a heavy duty clamp in industrial applications, in which case it would be fabricated from steel. | The invention relates to a clamp comprising a first C-shaped jaw having first and second limbs and an interconnecting bight portion. A second jaw is mounted pivotably to the second limb, and a releasable ratchet-and-pawl arrangement is provided for locking the second jaw relative to the first jaw in a number of degrees of closure. A finger-actuable tab is provided on the pawl for releasing the pawl from the ratchet and allowing bidirectional pivoting of the second jaw. The first limb is provided with a circular aperture and the second jaw is arranged to urge material to be clamped between the first and second jaws through the cavity, so as to increase the effectiveness of clamping. The material which has passed through the cavity also serves as a cushion. The clamp is particularly suited for use as a diaper clamp. | 8 |
CROSS REFERENCE TO RELATED DOCUMENT
The present application claims the benefit of Japanese Patent Application No. 2006-99193 filed on Mar. 31, 2006, the disclosures of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Technical Field of the Invention
The present invention relates generally to a gas sensor which may be employed in measuring the concentration of a selected component of exhaust gasses emitted from automotive engines, and more particularly to an anti-corrosion structure of such a gas sensor.
2. Background Art
Japanese Patent First Publication No. 10-10082 discloses a gas sensor to be installed in an exhaust pipe of an internal combustion engine for automotive vehicles to measure the concentration of a given gas component of exhaust emissions. FIG. 8 shows such a type of a gas sensor 9 .
The gas sensor 9 consists essentially of a sensor element (not shown) to measure the concentration of a gas (will also be referred to below as a measurement gas), a housing (not shown) in which the sensor element is retained, and an air cover assembly 94 joined to a base end of the housing.
The air cover assembly 94 is, as illustrated in FIGS. 8 and 9 , made up of an inner cover 941 and an outer cover 942 . The inner cover 941 is joined to the base end of the housing. The outer cover 942 surrounds a base end portion (i.e., an upper end portion, as viewed in the drawings) of the inner cover 941 .
The inner cover 941 and the outer cover 942 have portions 943 crimped circumferentially thereof.
However, when air is introduced into the gas sensor 9 from air inlets 945 formed in a base end portion of the outer cover 942 , water 7 may enter a clearance between the inner cover 941 and the outer cover 942 along a path, as indicated by a thick line W and accumulate, as clearly illustrated in FIG. 9 , especially in a clearance 96 near the crimped portions 943 , which will lead to the corrosion of an interface 8 between the inner cover 941 and the outer cover 942 . Specifically, when the water 7 accumulates in the clearance 96 , it results in a variation in concentration of oxygen between the clearance 96 and the interface 8 to facilitate or promote the transfer of metal ions from the inner and outer covers 941 and 942 , thereby causing the interface 8 to be eroded.
SUMMARY OF THE INVENTION
It is therefore a principal object of the invention to avoid the disadvantages of the prior art.
It is another object of the invention to provide an improved structure of a gas sensor designed to minimize gap corrosion between an inner cover and an outer cover of an air cover assembly.
According to one aspect of the invention, there is provided a gas sensor which may be employed in measuring the concentration of a component of exhaust gasses emitted from automotive engines. The gas sensor comprises: (a) a sensor element sensitive to a gas to produce a signal as a function of concentration of the gas, the sensor element having a length with a top end and a base end opposite the top end; (b) a housing in which the sensor element is retained, the housing having a top end and a base end opposite the top end; (c) an air cover assembly having a top end and a base end opposite the top end, the air cover assembly being made up of an inner cover and an outer cover, the inner cover being secured to the base end of the housing, the outer cover surrounding the inner cover and being joined to the inner cover through at least one crimped portion; (d) an air inlet formed in a portion of the air cover assembly which is closer to the base end of the air cover assembly than the crimped portion, the air inlet being designed to admit air into the air cover assembly; and (e) an air chamber defined by the crimped portion between the inner and outer covers of the air cover assembly from the crimped portion circumferentially of the air cover assembly. The air chamber is exposed outside the air cover assembly at a side opposite the air inlet across the crimped portion to define a water drain path establishing fluid communication between the air inlet and outside the air cover assembly.
The crimped portion is formed to occupy only a portion of the circumference of the air cover assembly, thereby defining the air chamber in which the water drain path extends from the air inlet to outside the air cover assembly. When the water enters at the air inlet, it will flow between the inner and outer covers along the water drain path and drain out of the air cover assembly, thereby minimizing gap corrosion between the inner and outer covers of the air cover assembly.
According to another aspect of the invention, there is provided a gas sensor which comprises: (a) a sensor element sensitive to a gas to produce a signal as a function of concentration of the gas, the sensor element having a length with a top end and a base end opposite the top end; (b) a housing in which the sensor element is retained, the housing having a top end and a base end opposite the top end; (c) an air cover assembly having a top end and a base end opposite the top end, the air cover assembly being made up of an inner cover and an outer cover, the inner cover being secured to the base end of the housing, the outer cover surrounding the inner cover and being joined to the inner cover through a crimped portion which extends over the whole of a periphery of the air cover assembly; (d) an air inlet formed in a portion of the air cover assembly which is closer to the base end of the air cover assembly than the crimped portion, the air inlet being designed to admit air into the air cover assembly; and (e) a water drain hole formed in the air cover assembly to establish fluid communication of outside the air cover assembly with a clearance extending from the crimped portion to the air inlet between the inner and outer covers of the air cover assembly.
When the water enters at the air inlet, it will flow between the inner and outer covers and drain out of the air cover assembly from the water drain hole, thereby minimizing gap corrosion between the inner and outer covers of the air cover assembly.
In the preferred mode of the invention, the drain hole is formed in the outer cover of the air cover assembly to extend from an edge of the crimped portion toward the air inlet, thereby avoiding accumulation of the water around the crimped portion between the inner and outer covers to facilitate ease of draining of the water.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will be understood more fully from the detailed description given hereinbelow and from the accompanying drawings of the preferred embodiments of the invention, which, however, should not be taken to limit the invention to the specific embodiments but are for the purpose of explanation and understanding only.
In the drawings:
FIG. 1 is a longitudinal sectional view which shows an internal structure of a gas sensor according to the first embodiment of the invention;
FIG. 2 is a partially enlarged sectional view, as circled by a broken line B in FIG. 1 , which shows an inner and an outer cover of an air cover assembly of the gas sensor, as illustrated in FIG. 1 ;
FIG. 3 is a transverse sectional view, as taken along the line A-A in FIG. 1 ;
FIG. 4 is a longitudinal sectional view which shows an internal structure of a gas sensor according to the second embodiment of the invention;
FIG. 5 is a partially enlarged sectional view, as circled by a broken line C in FIG. 4 , which shows an inner and an outer cover of an air cover assembly of the gas sensor, as illustrated in FIG. 4 ;
FIG. 6 is a partially side view which shows an air cover assembly of the gas sensor of FIG. 4 ;
FIG. 7 is a graph which shows results of corrosion tests;
FIG. 8 is a partially longitudinal sectional view which shows an internal structure of a conventional gas sensor; and
FIG. 9 is a partially enlarged sectional view, as circled by a broken line D in FIG. 8 , which shows an inner and an outer cover of an air cover assembly of the gas sensor, as illustrated in FIG. 8 .
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to the drawings, wherein like reference numbers refer to like parts in several views, particularly to FIGS. 1 , 2 , and 3 , there is shown a gas sensor 1 according to the first embodiment of the invention which may be used in measuring the concentration of a given component of exhaust emissions of automotive engines. For instance, the gas sensor 1 may be designed as an O 2 sensor, an A/F sensor, or a NOx sensor.
The gas sensor 1 consists essentially of a sensor element 2 sensitive to a gas to be measured (which will also be referred to as a measurement gas below) to produce an electrical signal as a function of the concentration of the measurement gas, a housing 3 in which the sensor element 2 is retained, and an air cover assembly 4 joined to a base end (i.e., an upper end, as viewed in FIG. 1 ) of the housing 3 .
The air cover assembly 4 is made up of an inner cover 41 and an outer cover 42 . The inner cover 41 is secured at an end thereof to the base end of the housing 3 . The outer cover 42 is placed to surround a base end portion (i.e., an upper end portion, as viewed in FIG. 1 ) of the inner cover 41 .
The air cover assembly 4 has formed therein air inlets 5 through which air is admitted inside the gas sensor 1 .
The air cover assembly 4 has, as clearly shown in FIGS. 1 and 3 , joints 43 by which the inner and outer covers 41 and 42 are connected together. The joints 43 are, as can be seen in FIG. 1 , located closer to the top (i.e., a lower end, as viewed in the drawing) of the gas sensor 1 than the air inlets 5 and formed by elastically deforming or crimping, for example, four circumferentially spaced portions of each of the inner and outer covers 41 and 42 inwardly. The joints 43 will also be referred to as crimped portions below. The crimped portions 43 define, as clearly illustrated in FIG. 3 , air chambers 44 between adjacent two joints thereof which open outside the air cover assembly 4 at the top end of the outer cover 42 .
The sensor element 2 is, as clearly shown in FIG. 1 , of a cup-shape with a bottom.
The housing 3 has formed in an outer periphery thereof a thread 31 for installation of the gas sensor 1 in, for example, an exhaust pipe (not shown) of the automotive engine. When the gas sensor 1 is installed in the exhaust pipe, the top end portion (i.e. the lower end portion, as viewed in FIG. 1 ) of the gas sensor 1 extends downward within the exhaust pipe, while the base end portion (i.e., the upper end portion) of the gas sensor 1 extends upward outside the exhaust pipe.
The outer cover 42 has formed in the base end portion thereof air intake openings 425 through which the air is to be admitted thereinto.
The inner cover 41 is made up of a large-diameter portion 411 extending to the top end thereof and a small-diameter portion 412 extending to the base end thereof. The inner cover 41 has formed in the small-diameter portion 412 air intake holes 415 which face the air intake openings 425 radially of the air cover assembly 4 .
The air cover assembly 4 also has a ventilation filter 50 made of, for example, a water-repellent filter 50 nipped between the inner cover 41 and the outer cover 42 . The ventilation filter 50 constitutes the air inlets 5 along with the air intake openings 425 and the air intake holes 415 .
The air cover assembly 4 , as described above, has the four crimped portions 43 which are located at equi-intervals in the circumferential direction thereof to define the four air chambers 44 , as clearly illustrated in FIG. 3 , which are identical in size or volume with each other.
A rubber bush 13 is, as illustrated in FIG. 1 , fitted in the base end of the air cover assembly 4 . The rubber bush 13 retains therein leads 12 which are connected electrically with the sensor element 2 and is held by crimping the outer cover 42 inwardly to establish a liquid-tight seal in the base end of the gas sensor 1 .
The gas sensor 1 is designed to have a drain path for water entering at the air inlets 5 , as described below.
When the vehicle is splashed with water during traveling or washing, water may enter, as indicated by an arrow W, between the inner cover 41 and the outer cover 42 from the air inlets 5 . The water then flows, as illustrated in FIG. 2 , toward the top end or downward of the gas sensor 1 , enters the air chambers 44 , and drains outside the air cover assembly 4 . When hitting one of the crimped portions 43 , the water, as indicated by arrows W in FIG. 3 , flows into an adjacent one(s) of the air chambers 44 and then drains outside the air cover assembly 4 . This avoids the accumulation of the water between the inner cover 41 and the outer cover 42 , thus preventing the gap corrosion therebetween.
The number of the crimped portions 43 is not limited to four. The air cover assembly 4 may alternatively have at least one crimped portion 43 to join the inner cover 41 and the outer cover 42 together.
FIGS. 4 to 6 show the gas sensor 1 according to the second embodiment of the invention which is different from the first embodiment in that the air cover assembly 4 has one crimped portion 45 which extends over the overall circumference of the air cover assembly 4 to join the inner and outer covers 41 and 42 . The crimped portion 45 is, like the first embodiment, located closer to the top end of the gas sensor 1 than the air inlets 5 .
The outer cover 42 has at least one drain hole 421 which is, as clearly illustrated in FIG. 6 , formed to extend vertically across an upper edge of the crimped portion 45 closer to the base end of the air cover assembly 4 . The water having flowed to the crimped portion 45 between the inner and outer covers 41 and 42 escapes, as indicated by an arrow W in FIG. 5 , outside the air cover assembly 4 from the drain hole 421 .
The crimped portion 45 of the air cover assembly 4 , as referred to herein, is made up of portions of the inner and outer covers 41 and 42 which are, as illustrated in FIG. 5 , pressed inwardly into direct abutment with each other in a range R.
Other arrangements are identical with those in the first embodiment, and explanation thereof in detail will be omitted here.
The inventor of this application performed corrosion tests in comparison of the gas sensor 1 with a conventional type of gas sensor.
The inventor prepared two types of test samples: one is the gas sensor 1 of the invention, and the other is a conventional type. Specifically, the inventor prepared, as can be seen from a graph of FIG. 7 , four No. 1 test samples identical in structure with the one illustrated in FIG. 8 and sixteen No. 2 test samples identical in structure with the gas sensor 1 , and broken down the No. 2 test samples into four groups.
Each of the corrosion tests was performed by installing one of the test samples in a pipe by screwing a thread (like the one, as denoted at 31 in FIG. 1 ) thereinto, heating the pipe for eighteen minutes until the thread reaches 300° C., and then spraying salt water containing 5% by weight of salt over the whole of a portion of the test sample exposed outside the pipe. This cycle was repeated 300 times for the No. 1 test samples and the first group of the No. 2 tests samples, 600 times for the second group of the No. 2 test samples, 900 times for the third group of the No. 2 test samples, and 1200 times for the fourth group of the No. 2 test samples.
The air cover assembly of each of the test samples is made of stainless steel (SUS304).
After the above corrosion tests, the inventor disassembled the air cover assembly of each of the test samples, removed extraneous matter from opposed surfaces of the inner and outer covers of the air cover assembly, and observed the surfaces visually using a microscope to check them for cracks. When the crack was found in either of the surfaces of the inner and outer covers, it was decided that the surfaces of the inner and outer covers were corroded. This is because usually, when corrosion occurs between the inner and outer covers, it will cause the opposed surfaces of the inner and outer covers to darken, but however, it is difficult to determine whether such darkening has arisen from corrosion or stains on the surfaces. Therefore, when the crack arising from the corrosion was visually perceived, corrosion was determined as having occurred between the inner and outer covers.
Results of the corrosion tests are plotted in the graph of FIG. 7 . The graph shows that when subjected to 300 cycles (100 hours) of the corrosion test, all the No. 1 test samples are cracked, and when subjected to 900 cycles (300 hours) of the corrosion test, the No. 2 test samples are all not yet cracked, however, when subjected to 1200 cycles (400 hours) of the corrosion test, two of the fourth group of the No. 2 test samples are cracked. It is, therefore, found that the structure of the gas sensor 1 is useful for avoiding corrosion between the inner and outer covers 41 and 42 of the air cover assembly 4 which usually leads to cracks.
While the present invention has been disclosed in terms of the preferred embodiments in order to facilitate better understanding thereof, it should be appreciated that the invention can be embodied in various ways without departing from the principle of the invention. Therefore, the invention should be understood to include all possible embodiments and modifications to the shown embodiments which can be embodied without departing from the principle of the invention as set forth in the appended claims. | An anti-corrosion structure of a gas sensor is provided. The gas sensor includes a hollow cylindrical air cover assembly made up of an inner and an outer cover. The air cover assembly has formed therein air inlets through which air is admitted into the gas sensor. The inner and outer covers are joined together through at least one crimped portion which defines a water drain path extending from the air inlets to outside the air cover assembly, thereby draining the water entering at the air inlets out of the gas sensor. This avoids accumulation of the water between the inner and outer covers to minimize gap corrosion therebetween. | 6 |
FIELD OF THE INVENTION
[0001] The present invention relates generally to molding (often referred to as trim or wall base) that is located at the base of interior walls. More particularly, the present invention relates to a corner section of trim and a method for attaching it to a corner defined by two interior walls, the corner section may be used in accordance many types of wall base as well as a stackable trim molding system where the molding is made of a resilient man-made material.
BACKGROUND OF THE INVENTION
[0002] Molding (or trim) is often placed at a base section of a wall, where the wall meets the floor. The molding receiving proposed modifications and improvements is commonly referred to as wall base, cove base, base board, base molding, mop board, trim, and/or skirting. Molding is used whether a floor be hardwood, carpet, or resilient flooring to provide a transition between the wall and the flooring. The trim can provide several useful functions. For example, if the wall is painted, the painting can extend to nearly the floor and then be covered by trim creating a clean, crisp line between the trim and the paint. The same can be true for when the wall is wallpapered. However, if a wall is to be repainted, to achieve a crisp line between the end of the wall, the trim must be taped prior to painting, a slow and steady approach to carefully painting the wall but not contacting the trim must be adopted or the trim must be removed before the paint is applied. These methods are laborious. In the case of removing the trim, often the act of removing the trim causes it to be destroyed, and new trim must be applied after the wall is repainted. These methods can be time-consuming and costly.
[0003] Other problems with existing trim is that the trim is susceptible to damage. For example, often trim is made of wood, which can crack or break, or be gouged which necessitates the trim being repaired or replaced. Another problem associated with trim is that if a floor surface is to be replaced, whether it be replacing the carpet, or adding carpet over an uncarpeted floor, or any other type of floor replacement, often the trim must be replaced. The trim often needs replacement because the new flooring will have a different height than the old flooring, or the act of removing the flooring will cause the trim to crack and break. Wood trim can be expensive and labor intensive to be treated whether by painting or being stained, or otherwise given a surface treatment in order to preserve the wood. Further, wood trim must be machined in order to give the trim contours such as beveled edges or other contours that are often desirable. The need to work the wood trim of course, can increase its costs.
[0004] Another problem encountered when installing trim systems is how to apply a wall base to a corner defined by the intersection of two walls. The problem is compounded by the fact that corners can be inside or outside corners, and each type of corner must be dealt with differently.
[0005] Currently, when wall base or other trim is installed at a location having a corner, a variety of methods are employed. Some methods require cutting and fitting on site where the installers, giving the primary responsibility of altering some of the existing base material to create the corner. This usually ends up with mixed results, depending upon the experience and ability of the particular installer.
[0006] In some of these cases, the wall base material is grooved on the back and wrapped around the corner where the point of the corner coincides with the groove. In this instance, some portions of the wall base may be permanently distorted and sometimes discolored at the apex of the corner due to stress on the wall base material.
[0007] In many cases, the resilient wall base inherently is biased to return to a straight position. This biasing feature of the wall base may result in the base pulling away from the wall when bent around a corner and, leaving an unsightly gap.
[0008] Recently, the marketplace has seen an increase of resilient base material that is too thick for either of these installation methods. In such an instance, an installer is required to miter cut and fit the wall base on site. In many cases, this requires the abilities that may be outside the realm of many flooring and trim installers.
[0009] In some instances, corner blocks or other factory-produced materials are used to cover corners. This approach can result in a dissimilar material used at the corner that does not match the wall base material. The corner blocks may be rigid and may be prone to be knocked loose by pedestrian traffic or floor maintenance equipment.
[0010] Accordingly, it is desirable to provide a trim molding system and method that can overcome some of the problems associated with traditional trim systems. For example, it would be desirable to provide corner pieces for use in a trim system to alleviate the need for installers to spend significant time and effort to customized wall base or other types of trim at corners. Further, it would be desirable to provide corner pieces of trim to give a finished, good workmanship type appearance at corner installations.
SUMMARY OF THE INVENTION
[0011] The foregoing needs are met, to a great extent, by the present invention, wherein in one aspect an apparatus and method is provided to provide corner pieces for use in a trim system to alleviate the need for installers to spend significant time and effort to customized wall base or other types of trim at corners. An aspect of some embodiments of the invention is to provide corner pieces of trim to give a finished, good workmanship type appearance at corner installations.
[0012] In accordance with one embodiment of the present invention, a trim section is provided. The trim section includes: a resilient corner section having a front and back; a first and second generally planer surfaces intersecting at an angle on the back of the resilient corner section; and first and second tabs connecting to the resilient corner section having a cross sectional thickness less than a cross sectional thickness of the corner section.
[0013] In accordance with another embodiment of the present invention, a method for installing a molding system is provided. In some embodiments of the invention, the method includes: mounting the corner piece of trim to a wall corner defined by two wall intersecting at an angle with respect to each other; and mounting a tab associated with the corner piece of trim to a wall, wherein an angled corner defined by the walls is covered by the corner piece of trim and the angled corner is fitted to a surface on the corner piece of trim complimenting the angled corner.
[0014] In accordance with yet another embodiment of the present invention, a trim section is provided. The trim section includes: a resilient corner section; a first and second generally planer surfaces intersecting at an angle on the corner section; and means for securing the resilient corner section to a wall, wherein the means for securing the resilient corner section to a wall forms a substantially planner surface with the at least one of the first and second generally planer surfaces.
[0015] There has thus been outlined, rather broadly, certain embodiments of the invention in order that the detailed description thereof herein may be better understood, and in order that the present contribution to the art may be better appreciated. There are, of course, additional embodiments of the invention that will be described below and which will form the subject matter of the claims appended hereto.
[0016] In this respect, before explaining at least one embodiment of the invention in detail, it is to be understood that the invention is not limited in its application to the details of construction and to the arrangements of the components set forth in the following description or illustrated in the drawings. The invention is capable of embodiments in addition to those described and of being practiced and carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein, as well as the abstract, are for the purpose of description and should not be regarded as limiting.
[0017] As such, those skilled in the art will appreciate that the conception upon which this disclosure is based may readily be utilized as a basis for the designing of other structures, methods and systems for carrying out the several purposes of the present invention. It is important, therefore, that the claims be regarded as including such equivalent constructions insofar as they do not depart from the spirit and scope of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 is a perspective view illustrating a resilient trim system and covering apparatus for an inside corner according to an embodiment of the invention.
[0019] FIG. 2 is a top view of a resilient corner section.
[0020] FIG. 3 is a side view of the resilient corner section shown in FIG. 2 .
[0021] FIG. 4 is a rear view of the resilient corner section shown in FIG. 2 .
[0022] FIG. 5 is a perspective view illustrating a resilient trim system and cornering apparatus for an outside corner, according to an embodiment of the invention.
[0023] FIG. 6 is a top view of a resilient corner section for an outside corner.
[0024] FIG. 7 is a side view of the resilient corner section shown in FIG. 6 .
[0025] FIG. 8 is a rear view of the resilient corner section shown in FIG. 6 .
DETAILED DESCRIPTION
[0026] The many features and advantages of the invention are apparent from the detailed specification, and thus, it is intended by the appended claims to cover all such features and advantages of the invention which fall within the true spirit and scope of the invention. Further, since numerous modifications and variations will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation illustrated and described, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope of the invention.
[0027] The invention will now be described with reference to the drawing figures, in which like reference numerals refer to like parts throughout. An embodiment in accordance with the present invention provides an apparatus and method for covering a corner with a resilient base (trim) using a corner piece of wall base. Some embodiments of the invention may be useful for covering an outside corner and other embodiments of the invention may be useful for covering an inside corner.
[0028] FIGS. 1-4 illustrate one embodiment of the invention that includes a corner piece 12 configured for attaching to an inside-type corner. The term, “inside”, refers to the fact that corner piece 12 is fit inside a space defined by the corner as shown in FIG. 1 . FIGS. 5-8 will illustrate another embodiment of the invention where a corner piece 12 is fit to an outside corner. The term, “outside corner”, refers to the fact that the corner piece 12 is placed in a space outside of the corner defined by the walls 20 , 22 as shown in FIG. 5 . In addition, corners having angles of less than equal to and greater than 90° may be covered using apparatus described herein. FIGS. 1-4 will be explained first and then FIGS. 5-8 will be explained.
[0029] An embodiment of the present inventive apparatus is illustrated in FIG. 1 . FIG. 1 illustrates a resilient (flexible) molding system 10 . A flexible molding system 10 shown in FIG. 1 includes a corner piece 12 , a wall base 14 , a base shoe 16 , and a top trim piece 18 . The flexible molding system also includes an adhesive 19 which adheres the flexible molding system to walls 20 , 22 . The flexible molding system 10 is attached to the base of the walls 20 , 22 , and is adjacent to and sits upon a floor 24 .
[0030] The corner piece 12 is suited to be used with elements of a flexible molding system and method as shown and described in U.S. patent application Ser. No. 10/991,502, titled Stackable Trim Molding System and Method, filed Nov. 19, 2004, which is incorporated herein by reference in its entirety. However, the corner piece 12 , or other apparatus and methods in accordance with the invention are suitable for use with other trim systems, molding systems and wall base systems and are in no way limited to specific systems described in the application mentioned above.
[0031] As shown in FIG. 2 , the corner piece 12 includes a main section 26 . The main section 26 has a front 28 and a back 30 . For the purposes of this document, the term “front” 28 refers to the part of the corner piece 12 that will be exposed when the corner piece 12 is installed at a corner, and the back 30 is the part of the corner piece 12 that will be butted up against and adhered to the walls 20 , 22 , defining the corner.
[0032] On the back 30 of the corner piece 12 , is a first surface 32 and a second surface 34 . The first and second surfaces 34 intersect with each other in some embodiments at substantially a right angle. Because the corner piece 12 is flexible and resilient, it may accommodate corners where the walls 20 and 22 do not meet to form a right angle. However, if the angle varies too far from a 90° angle, then corner pieces 12 may be manufactured where the first 32 and second surface 34 come together at a different angle to accommodate a corner having an obtuse or acute angle defined by the walls 20 , 22 .
[0033] The first surface 32 and the second surface 34 are generally flat although they may include ridges or grooves, be scored, or have other type of surface phenomena in order to provide a desired surface for facilitating adhesion of an adhesive 19 between the corner piece 12 and the walls 20 , 22 .
[0034] A first tab 36 and second tab 38 are located on and attached to the corner piece 12 . The first tab 36 is attached to the main section 26 of the corner piece 12 to provide a generally continuous surface with the first surface 32 . Likewise, the second tab 38 is attached to the main section 26 of the corner piece 12 to provide a generally continuous surface with the second surface 34 . Again, the tabs 36 and 38 may include grooves or ridges, scoring any other surface phenomena in order to facilitate adhesion to the walls 20 , 22 .
[0035] The front 28 of the main section 26 may be contoured in a decorative manner in order to enhance the visual appearance of the corner piece 12 .
[0036] FIG. 3 is a side view of the corner piece 12 shown in FIGS. 1-4 . FIG. 3 illustrates the back 30 and front 28 sides of the corner piece 12 . Tabs 38 and 36 and the bottom surface 42 of the corner piece 12 are also visible in FIG. 3 .
[0037] In some embodiments of the invention, in order to size the corner piece 12 to a desired height, an installer may cut with a saw or other suitable means, the corner piece 12 near the bottom end 42 .
[0038] Some embodiments of the invention include angled portions 40 of the tabs 38 and 36 as seen in FIGS. 1, 3 and 4 . In some embodiments of the invention, angled portions 40 are used on the tabs 38 , 36 to help in reducing the likelihood of a gap forming between a walls 20 , 22 and a top piece 18 (or wall base 16 when top trim is not used) due to the tab 36 or 38 existing between top piece of trim 18 or wall base 16 and the walls 20 , 22 . An unsightly gap may be avoided by connecting the top trim 18 directly to the walls 20 , 22 without having, or at least minimally having a portion of the tab 36 in between the top trim 18 and the walls 20 , 22 .
[0039] Thus, the angled portions 40 are incorporated in some embodiments to reduce the likelihood of creating a gap between the top trim 18 (or wall base 14 ) and the walls 20 , 22 .
[0040] With reference now to FIG. 4 , the back side 30 of the corner piece 12 is shown. As shown in FIG. 4 , the first surface 32 , including a back surface of the tab 36 , creates a generally plainer surface, and is ready for application of an adhesive 19 .
[0041] In some embodiments of the invention, the adhesive 19 may be a latex adhesive, similar to adhesives commonly used for installing other types of trim. Other ways of installing the corner piece 12 to a wall 20 , 22 can include glue (perhaps factory applied) that can be applied to the back 30 of the corner piece 12 . The glue may be protected until installation by a removable release paper that is removed to expose the glue prior to installation. In other embodiments of the invention, a double-faced scrim-reinforced tape is used. The tape is carried on a release paper. It is attached to the back 30 of the corner piece 12 , then the paper is removed, and the corner piece 12 is placed where desired.
[0042] In other embodiments of the invention, the corner piece 12 may be adhered to the walls 20 , 22 by use of any suitable adhesive or fastener in accordance with the present invention. As shown in FIGS. 1 and 5 , mechanical fasteners 39 may also be used. Mechanical fasteners can include nails, screws, staples or any other mechanical-type fastener. Mechanical fasteners 39 may extend through the tabs 36 , 38 and through the walls 20 , 22 to attach the corner piece 12 to the walls 20 , 22 . Some embodiments of the invention may include adhesives and mechanical fasteners. Optionally, the corner piece may be fastened to the floor 24 (see FIG. 1 ) by adhesive and/or mechanical fastener.
[0043] FIG. 5 is an illustration of an apparatus in accordance with one embodiment of the present invention where a corner piece 12 is fitted to an outside corner defined by walls 20 , 22 . The corner piece 12 has a front side 28 and a back side 30 . The back side 30 attaches to a corner defined by two walls 20 , 22 , as shown.
[0044] Attached to the corner piece 12 are a first tab 36 and a second tab 38 . The tabs 36 and 38 are connected to walls 20 , 22 , respectively. The tabs 36 , 38 may be connected to the walls 20 , 22 , by an adhesive 19 such as those described above, or by mechanical fasteners 39 as previously described. An adhesive may also be applied to the main section 26 of the corner piece 12 as well as the tabs 36 , 38 . A wall base 14 is adhered to a wall 20 and butts up against the main section 26 of the corner piece 12 . Optionally, a base shoe 16 is located below the wall base 14 .
[0045] In some embodiments of the invention, the base shoe 16 may include a carpet notch 46 which permits carpet to be placed in the notch 46 in order to provide a smooth transition between carpet and the base shoe 16 . An optional trim piece 18 is mounted above the wall base 14 . The top trim piece 18 abuts against the main section 26 of the corner piece 12 . The wall base 14 , the base shoe 16 and the corner piece 12 may be the same or different colors and have different contours in order to improve the aesthetic view of the trim system. The corner piece 12 may also be decoratively contoured and/or colored.
[0046] The surface finish on the corner piece 12 wall base 14 , base shoe 16 and top trim 18 may be one that will permit paint to be applied to it.
[0047] In some embodiments of the invention, the corner piece 12 is also equipped with a carpet notch 44 in order to allow carpet to be placed in the notch 44 to provide a smooth transition between carpet and the corner piece 12 . While the carpet notches 44 , 46 are illustrated in embodiments where the corner piece 12 is adjusted to fit an outside corner, certainly carpet notches 44 , 46 are not limited to such embodiments but may be also used in or be found in embodiments adapted for inside corners as well.
[0048] FIG. 6 is a top view of the corner piece 12 according to an embodiment of the invention used for outside corners. The corner piece 12 includes a front side 28 that is rounded to soften the edges of the corner defined by the walls 20 , 22 . On the back 30 side of the corner piece 12 , there is a first surface 32 and a second surface 34 , which are extended from the 26 by the first tab 36 and the second tab 38 .
[0049] FIG. 7 is a side view of the corner piece 12 illustrated in FIG. 6 . The front side 28 is visible in FIG. 7 , and the front side of tab 36 is also illustrated. The angle portion 40 of tab 36 is shown descending from the main section 26 of the corner piece 12 to the end of tab 36 . The bottom surface 42 is substantially flat and configured to rest on a floor 24 , shown in FIG. 5 .
[0050] FIG. 8 is a rear view of the corner piece 12 , shown in FIG. 6 . In the rear view, tabs 36 , 38 are shown. The first surface 32 is shown to be substantially flat and contiguous with the back surface of tab 36 . Tab 38 is also illustrated and shows a substantially flat surface contiguous with the second surface 34 .
[0051] The installation of a corner piece 12 will now be described according to some embodiments of the invention. In some embodiments of the invention, corner piece 12 is used as part of the system that includes a wall base 14 , an optional base shoe 16 , and an optional top trim piece 18 , as illustrated in FIGS. 1 and 5 . An adhesive is applied to the back 30 of the corner piece 12 , particularly to the first and second surfaces 32 , 34 (including back of the first and second tabs, 36 , 38 ). Alternatively, the adhesive can be applied to the walls 20 , 22 , and then the corner piece 12 can be fitted so that a corner defined by the walls 20 , 22 fit around a corner defined by the intersection of the first and second surfaces 32 , 34 , on the corner piece 12 . In some optional embodiments of the invention, mechanical fasteners may be used to secure the corner piece 12 in place. Any suitable method of securing the corner piece 12 in place is within the scope of the invention.
[0052] In some embodiments of the invention, the corner piece 12 may be trimmed by cutting the corner piece to a desired size before its installation. In some embodiments of the invention, the corner piece 12 may be trimmed by cutting the bottom 42 of the corner piece 12 . In other embodiments of the invention, the corner piece can be trimmed at the top, and then the corner piece 12 can be applied to the walls 20 , 22 , as described.
[0053] Once the corner piece 12 is installed, an adhesive may be applied to the back part of the tabs 36 , 38 , and then a wall base 14 can be applied as well as a base shoe 16 and top trim piece 18 (optionally the adhesive may be applied to the back of the wall base 14 , the optional base shoe 16 and optional top trim 18 ).
[0054] In some optional embodiments of the invention, a carpet notch 44 may be found in the corner piece 12 . Carpet notches may also be found in some optional embodiments of the invention in the base shoe 16 or, alternatively, wall base 14 . In embodiments of the invention, which include carpet notches 44 , 46 , the carpet notches provide a place for carpet to be located once the corner piece 12 and the base shoe 16 have been installed.
[0055] The many features and advantages of the invention are apparent from the detailed specification, and thus, it is intended by the appended claims to cover all such features and advantages of the invention which fall within the true spirit and scope of the invention. Further, since numerous modifications and variations will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation illustrated and described, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope of the invention. | An apparatus and method for covering a corner with trim includes a trim section. The trim section includes a resilient corner section having, a first and second generally-planar surfaces intersecting at an angle on the back of the resilient corner section and first and second tabs having a cross-sectional thickness less than a cross-sectional thickness of the corner section. The method for installing a molding system includes mounting the corner piece of trim to a wall corner defined by two walls intersecting at an angle with respect to each other and mounting a tab associated with the corner piece or trim to the wall, wherein an angled corner defined by the walls is covered by the corner piece of trim, and the angled corner is fitted to a surface on the corner piece of trim complementing the angled corner. | 4 |
FIELD OF THE INVENTION
[0001] This invention relates to novel analogues of camptothecin and will have application to highly lipophilic camptothecin derivatives (HLCDs) that include a germanium-containing substitution moiety at one or more of C7, C9, C10, C11, C12 or C5 of the camptothecin scaffold.
BACKGROUND OF THE INVENTION
[0002] Camptothecin (CPT) and certain of its derivatives are potent antineoplastic agents that are currently the subject of numerous ongoing scientific investigations. Recently, the Untied States Food and Drug Administration (FDA) approved the first two CPT derivatives (Irinotecan and Topotecan, discussed below) for human use as therapy for various forms of solid neoplasms. The structure of camptothecin, with the colloquially accepted numbering scheme is shown below.
[0000]
[0003] Camptothecin was initially isolated in 1966 by Wall and Wani from Camptotheca accuminata, a Chinese yew. CPT was subsequently observed to have potent anti-cancer activity and was introduced into human clinical trials in the late-1970's. The closed E-ring lactone form of CPT was noted to be very poorly water soluble (with only approximately 0.1 microgram of drug dissolving in 1 mL of water). In order for CPT to be administered in human clinical trials it was first formulated with sodium hydroxide. This formulation resulted in hydrolysis of the lactone E-ring of the camptothecin molecule and formed the water soluble carboxylate species. The sodium hydroxide formulation of CPT created a water soluble CPT species that permitted clinicians to administer larger doses of the drug to cancer patients undergoing Phase I and Phase II clinical trials. However, it was not learned until much later that the carboxylate form of CPT had approximately one-tenth or less of the anti-tumor potency of the lactone form of CPT. Clinical trials with sodium hydroxide formulated CPT were disappointing due to the frequently observed significant systemic toxicities and the lack of antineoplastic activity, and clinical studies of CPT were halted in the early-1980's.
[0004] Further clinical development of CPT derivatives was not pursued until the mid-1980s. At that time it was reported that CPT had a unique mechanism of action involving the inhibition of DNA synthesis and DNA replication by interactions with the ubiquitous cellular enzyme Topoisomerase I (Topo I). This new information about the mechanism of action of CPT derivatives rekindled the interest in developing new Topo I inhibitors as antineoplastic drugs and subsequently several research groups began attempting to develop new CPT derivatives for cancer therapy. In general, it was observed that, like CPT, many of its derivatives were also very poorly soluble in water (less than 1 μg/mL). This low water solubility greatly limited the practical clinical utility of the drug because prohibitively large volumes, of fluid had to be administered to the patient in order to provide an effective dose of the drug. Because of the potent antineoplastic activity and poor water solubility of CPT and many of its derivatives in water, a great deal of research effort was directed at generating new CPT derivatives that were water soluble. This research is discussed below.
[0005] As stated earlier, CPT and many of its derivatives (see, e.g., Wall and Wani, Camptothecin and Taxol: Discovery to Clinic-Thirteenth Bruce F. Cain Memorial Award Lecture. Cancer Res. 55:753-760 (1995)) are poorly water soluble and are also reportedly poorly soluble in a number of pharmaceutically-acceptable organic solvents as well. There are numerous reports of newly created water soluble derivatives of CPT (see, e.g., Sawada, S., Kingsbury, W. D., Luzzio, G. Synthesis and Antitumor Activity of Novel Water Soluble Derivatives of Camptothecin as Specific Inhibitors of Topoisomerase I. J. Med. Chem. 38:395-401 (1995)) which have been synthesized in an attempt to overcome some of the significant technical problems in drug administration of poorly water soluble camptothecins to patients with cancer. Several water soluble CPT derivatives have been synthesized in an attempt to address the poor water solubility and difficulties in administration to patients. Well known examples of these water-soluble CPT derivatives include: 9-dimethylaminomethyl-10-hydroxy camptothecin (Topotecan), 7-[(4-methylpiperazino)methyl]-10,11-ethylenedioxy camptothecin, 7-[(4-methylpiperazino)methyl]-10,11-methylenedioxy camptothecin, and 7-ethyl-10-[4-(1-piperidino)-1-piperidino]carbonyloxy camptothecin (Irinotecan or CPT-11).
[0006] Other substituted CPT derivatives with different solubility and pharmacologic properties have been synthesized as well; examples of these camptothecin derivatives include 9-amino camptothecin and 9-nitro camptothecin, which are poorly soluble in both aqueous and nonaqueous media and have been tested in humans. 9-nitro camptothecin is a prodrug of 9-amino camptothecin and spontaneously converts to 9-amino camptothecin in aqueous media and in vivo in mice, dogs and humans. See, e.g., Hinz, et al., Pharmacokinetics of the in vivo and in vitro conversion of 9-Nitro-20(S)-camptothecin to 9-Amino-20(S)-camptothecin in humans, dogs and mice. Cancer Res. 54:3096-3100 (1994).
[0007] The pharmacokinetic behavior of 9-nitro camptothecin and 9-amino camptothecin is similar to the water soluble camptothecin derivatives (Topotecan and Irinotecan) in that the plasma half-lives are much shorter than the more lipid soluble CPT derivatives. Another major problem with 9-amino camptothecin is that its chemical synthesis using the semi-synthetic method is carried out by nitration of CPT, followed by reduction to the amino group, which is a very low yield synthesis. In addition, 9-amino camptothecin is light-, heat-, and oxygen-sensitive; all of which render the production and stabilization of 9-amino camptothecin markedly difficult. The chemical decomposition reactions of 9-amino camptothecin can also result in the formation of compounds that exhibit a large degree of toxicity in nude mice; whereas pure 9-amino camptothecin is significantly less toxic.
[0008] Furthermore, 9-amino camptothecin is also difficult to administer to patients because it is poorly soluble in both aqueous and organic solvents. 9-nitro camptothecin is easier to produce and is more chemically stable, but with the chemical conversion to 9-amino camptothecin the drug is reportedly susceptible to MDR/MRP mediated drug resistance, which further limits its utility in the unfortunately common setting of drug resistant neoplasms. Based on pharmacokinetic behavior and chemical properties, 9-amino camptothecin is predicted to have reduced tissue penetration and retention relative to more lipid soluble camptothecin derivatives. Further, its poor solubility diminishes the amount of the drug that can cross the blood/brain barrier.
[0009] Of this diverse group of substituted CPT derivatives undergoing human clinical development, Irinotecan (CPT-11) has been one of the most extensively studied in Phase I and Phase II clinical trials in human patients with cancer. It is noteworthy that Irinotecan, which is a water soluble prodrug, is biologically inactive and requires activation by a putative carboxylesterase enzyme. The active species of Irinotecan is the depiperidenylated 10-hydroxy-7-ethyl camptothecin (claimed in Miyasaka, et al., U.S. Pat. No. 4,473,692 (1984)), which is also known as SN38. SN38 is a toxic lipophilic metabolite, which is formed by an in vivo bioactivation of Irinotecan by a putative carboxylesterase enzyme.
[0010] SN38 is very poorly soluble in water and has not been directly administered to human patients with cancer. Recently, it has been reported in human patients that SN38 undergoes further metabolism to form a glucuronide species, which is an inactive form of the drug with respect to antitumor activity, and also appears to be involved in producing human toxicity (e.g., diarrhea, nausea, leukopenia) and substantial interpatient variability in drug levels of the free metabolite and its glucuronide.
[0011] Irinotecan has been tested in human clinical trials in the United States, Europe and Japan. Nearly 100 patient deaths directly attributable to Irinotecan drug toxicity have been reported in Japan alone. The Miyasaka, et al., patents (U.S. Pat. Nos. 4,473,692 and 4,604,463) state that the object of their invention is to “provide 10-substituted camptothecins which are strong in anti-tumor activity and possess good absorbability in living bodies with very low toxicity” and “to provide new camptothecin derivatives which are strong in anti-tumor activity and possess good solubility in water and an extremely low toxicity”.
[0012] Having multiple drug-related human deaths and serious patient toxicity, is clearly a failure of the Miyasaka, et al., inventions to fulfill their stated objects. It is notable that tremendous interpatient variability with regard to drug levels of various forms, drug metabolism, certain pharmacokinetic properties and toxicity has been reported with the use of Irinotecan in human subjects with cancer. Parenteral administration of Irinotecan can achieve micromolar plasma concentrations of Irinotecan that, through metabolism to form SN38, can yield nanomolar concentrations of the active metabolite SN38. It has recently been reported in human subjects that SN38 undergoes further metabolism to form the SN38 glucuronide. See, e.g., Gupta, et al., Metabolic Fate of Irinotecan in Humans: Correlation of Glucuronidation with Diarrhea. Cancer Res. 54:3723-3725 (1994).
[0013] This further metabolic conversion of Irinotecan is important, since there is also reportedly large variability in the conversion of Irinotecan to SN38 and large interpatient variability in the metabolism of SN38 to form the inactive (and toxic) SN38 glucuronide in human subjects. See, e.g., Gupta, et al., Metabolic Fate of Irinotecan in Humans: Correlation of Glucuronidation with Diarrhea. Cancer Res. 54:3723-3725 (1994) and Ohe, Y., et al., Phase I Study and Pharmacokinetics of CPT-11 with 5-Day Continuous Infusion. NCI 84:972-974 (1992).
[0014] Since the amount of Irinotecan and SN38 metabolized is not predictable in individual patients, significant clinical limitations are posed and create the risk of life-threatening drug toxicity, and/or risk of drug inactivity due to five possible mechanisms: (i) conversion of greater amounts of Irinotecan to SN38; (ii) inactivation of SN38 by glucuronidation; (iii) conversion of SN38 glucuronide to free SN38; (iv) lack of antineoplastic activity due to the conversion of lesser amounts of Irinotecan to form SN38; and (v) lack of antineoplastic activity by more rapid and extensive conversion of SN38 to form the glucuronide species. It is important to note that even a doubling of the plasma concentration of the potent Irinotecan metabolite SN38 may result in significant toxicity, because free SN38 exhibits antineoplastic activity at nanomolar concentrations.
[0015] Another source of interpatient variability and toxicity is the in vivo de-glucuronidation of SN38 and similar CPT derivatives to produce a free and active species of the drug. Deglucuronidation of a CPT derivative that is susceptible to A-ring glucuronidation, such as SN38, results in an increase in the plasma or local tissue concentration of the free and active form of the drug, and if high enough levels were reached, patient toxicity, and even death may result.
[0016] In recent years, camptothecin development has expanded in several directions. The most interesting of these developments has occurred in the areas of silicon-containing camptothecins, also referred to as Karenitecins and silatecans, and in the development of camptothecins with a 7-membered E-ring, also referred to as homocamptothecins. The Assignee of the instant patent application has over forty three (43) United States and International Patents have issued on the Karenitecin series of HLCDs. One silicon-containing HLCD (Karenitecin®; BNP1350) has been or is currently in late-phase clinical trials in the United States, Europe, and Japan.
SUMMARY OF THE INVENTION
[0017] The present invention comprises novel HLCDs that have the following Formula (I):
[0000]
wherein R 1 is —Ge—R 7 R 8 R 9 ; lower alkylene-Ge-R 7 R 8 R 9 ; lower alkenylene-Ge—R 7 R 8 R 9 ; or lower alkynylene-Ge—R 7 R 8 R 9 ;
R 2 , R 3 , R 4 and R 5 are each individually hydrogen, lower alkyl, lower alkenyl, lower alkynyl, aryl, acyl, arylalkyl, arylalkenyl, arylalkynyl, amino, nitro, cyano, heterocycle, alkoxycarbonyl, amino-lower alkyl, nitro-lower alkyl, heterocycle-lower alkyl, —X-(lower alkylene, lower alkenylene, lower alkynylene, phenylene or benzylene)-SiR 10 R 11 R 12 , —X-(lower alkylene, lower alkenylene, lower alkynylene, phenylene or benzylene)-NR 13 R 14 , or OR 15 ;
R 6 and R 15 are each individually hydrogen or an oxygen protecting group;
R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 16 are each individually lower alkyl, aryl or a substituted analogue thereof;
X is sulfur or a bond; and
pharmaceutically-acceptable salts and prodrugs thereof.
[0024] The present invention also provides for pharmaceutical formulations that include the Formula (I) compound as active agent, combined with one or more pharmaceutically-acceptable solvents, excipients, fillers or diluents. The invention also provides for methods of treating cancer by administering a therapeutically effective amount of the Formula I compound, or a formulation thereof.
[0025] It is a principal object of this invention to provide for novel HLCDs.
[0026] Another object is to provide for pharmaceutical formulations of the novel HLCDs, and for methods of treating susceptible cancers by administering effective amounts thereof.
DETAILED DESCRIPTION OF THE INVENTION
[0027] The preferred embodiment herein described is not intended to be exhaustive or to limit the invention to the precise form disclosed. It is chosen and described to explain the principles of the invention, and its application and practical use to enable others skilled in the art to follow its teachings.
Definitions
[0028] “Scaffold” means the fixed part of the molecule of the general formula given.
[0029] “Fragments” or “Moieties” are the variable parts of the molecule, designated in the formula by variable symbols, such as R x , X, or other symbols. Fragments may consist of one or more of the following:
“C x -C y alkyl” means a straight or branched-chain aliphatic hydrocarbon containing as few as x and as many as y carbon atoms. Examples include “C 1 -C 6 alkyl”, which includes a straight or branched chain hydrocarbon with no more than 6 total carbon atoms, and C 1 -C 16 alkyl, which includes a hydrocarbon with as few as one up to as many as sixteen total carbon atoms, and others; “C x -C y alkylene” means a bridging moiety formed of as few as “x” and as many as “y” —CH 2 — groups; “C x -C y alkenyl or alkynyl” means a straight or branched chain hydrocarbon with at least one double bond (alkenyl) or triple bond (alkynyl) between two of the carbon atoms; “C x -C y alkoxy” means a straight or branched hydrocarbon chain with as few as x and as many as y carbon atoms, with the chain bonded to the scaffold through an oxygen atom; “Lower” when used in conjunction with any hydrocarbon chain, limits the number of carbon atoms in said chain to a total of six (6). By way of non-limiting example, “lower alkyl” means C 1 -C 6 alkyl. “Alkoxycarbonyl” means an alkoxy moiety bonded to the scaffold through a carbonyl; “Halogen” or “Halo” means chloro, fluoro, bromo or iodo; “Acyl” means —C(O)—X, where X is hydrogen, C x -C y alkyl, aryl, C x -C y alkenyl, C x -C y alkynyl, aryl, etc.; “Acyloxy” means —O—C(O)—X, where X is hydrogen, C x -C y alkyl, aryl, etc.; “C x -C y Cycloalkyl” means a hydrocarbon ring or ring system consisting of one or more rings, fused or unfused, wherein at least one of the ring bonds is completely saturated, with the ring(s) having from x to y total carbon atoms; “Aryl” means an aromatic ring or ring system consisting of one or more rings, preferably one to three rings, fused or unfused, with the ring atoms consisting entirely of carbon atoms; “Arylalkyl” means an aryl moiety as defined above, bonded to the scaffold through an alkyl moiety (the attachment chain); “Arylalkenyl” and “Arylalkynyl” mean the same as “Arylalkyl”, but including one or more double or triple bonds in the attachment chain; “Heterocycle” means a cyclic moiety of one or more rings, preferably one to three rings, fused or unfused, wherein at least one atom of one of the rings is a non-carbon atom. Preferred heteroatoms include oxygen, nitrogen and sulfur, or any combination of two or more of those atoms; and “Substituted” modifies the identified fragments (moieties) by replacing any, some or all of the hydrogen atoms with a moiety (moieties) as identified in the specification.
[0045] “Protecting groups” are those moieties which are attached to a particular atom, and which prevent reaction at that position of the scaffold under specified conditions. Examples of the above moieties are as follows:
C 1 -C 6 alkyl (i.e., a lower alkyl) includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, amyl and the like; C 2 -C 8 alkenyl or alkynyl includes vinyl, propenyl, butenyl, acetylenyl, propynyl, and other like moieties with one or more double and/or triple bonds; Alkoxy includes methoxy, ethoxy, propoxy, and the like; Alkoxycarbonyl includes methoxycarbonyl, ethoxycarbonyl, and others; Acyl includes formyl, acetyl, propionyl and others; Acyloxy includes formoxy, acetoxy, propionoxy, and the like; Cycloalkyl includes cyclopropyl, cyclobutyl, cyclohexyl, indanyl, dihydronaphthalenyl, cyclohexenyl, and the like; Aryl includes phenyl, naphthyl and anthracenyl, as well as substituted variants wherein one of the hydrogen atoms bonded to the ring atom is substituted by a halogen atom, an alkyl group, or another moiety; Arylalkyl includes benzyl, phenethyl, and the like; Arylalkenyl and arylalkynyl includes phenyl vinyl, phenylpropenyl, phenylacetylenyl, phenylpropynyl and the like; and Heterocycle includes furanyl, pyranyl, thionyl, pyrrolyl, pyrrolidinyl, prolinyl, pyridinyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, oxathiazolyl, dithiolyl, oxazolyl, isoxazolyl, oxadiazolyl, pyridazinyl, pyrimidinyl, pyrazinyl, piperazinyl, oxazinyl, thiazolyl, and the like.
[0057] Substitutions for hydrogen atoms to form substituted analogues include halo, alkyl, nitro, amino (also N-substituted, and N,N di-substituted amino), sulfonyl, hydroxy, alkoxy, phenyl, phenoxy, benzyl, benzoxy, benzoyl, and trifluoromethyl.
[0058] Protecting groups include specific moieties for protecting, in particular, nitrogen terminal moieties and oxygen terminal moieties. Protecting groups are well-known in the art and are described in detail in Kocienski, P., Protecting Groups, In: Foundations of Organic Chemistry (Thieme, 1994); and Greene, W., Protective Groups in Organic Synthesis (Wiley, Second Edition, 1990).
[0059] The compounds of the present invention are highly lipophilic camptothecin derivatives (HLCDs) of the following Formula (I):
[0000]
wherein R 1 is —Ge—R 7 R 8 R 9 ; lower alkylene-Ge—R 7 R 8 R 9 ; lower alkenylene-Ge—R 7 R 8 R 9 ; or lower alkynylene-Ge—R 7 R 8 R 9 ;
R 2 , R 3 , R 4 and R 5 are each individually hydrogen, lower alkyl, lower alkenyl, lower alkynyl, aryl, acyl, arylalkyl, arylalkenyl, arylalkynyl, amino, nitro, cyano, heterocycle, alkoxycarbonyl, amino-lower alkyl, nitro-lower alkyl, heterocycle-lower alkyl, —X-(lower alkylene, lower alkenylene, lower alkynylene, phenylene or benzylene)-SiR 10 R 11 R 12 , —X-(lower alkylene, lower alkenylene, lower alkynylene, phenylene or benzylene)-NR 13 R 14 , or OR 15 ;
R 6 and R 15 are each individually hydrogen or an oxygen protecting group;
R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 16 are each individually lower alkyl, aryl or a substituted analogue thereof;
X is sulfur or a bond; and
[0065] pharmaceutically-acceptable salts and prodrugs thereof.
[0066] The present invention also includes pharmaceutical formulations suitable for administration to mammalian subjects, particularly to human patients.
[0067] The Formula I compounds of the present invention are useful cytotoxic agents that will find particular use in treating various susceptible tumors. Accordingly, the invention also provides for methods of treating mammalian subjects, in particular human patients by administering a therapeutically effective amount of a Formula I compound or a formulation containing a Formula I compound to a patient having a susceptible tumor.
[0068] The Formula I compounds may be prepared according to the following Schemes:
[0000]
[0069] Scheme 1 illustrates the synthesis of the dioxolane germanium intermediate compound, which is used in the addition reaction to substitute the germanium-containing moiety onto the camptothecin scaffold. The synthesis is preferably accomplished through a Grignard reaction utilizing a magnesium suspension and halogenated reactants to achieve the desired substitution of the trisubstituted germanium for the corresponding halogen atom (shown in Scheme 1 as Bromine (Br)). Reaction specifics of the Grignard conversion are well-known, are set forth in the examples below and, in no manner, limit the present invention.
[0000]
[0070] Scheme 2 illustrates the substitution of the germanium-containing moiety at C7 of the camptothecin scaffold. The synthetic process for this substitution is similar to that disclosed in U.S. Pat. No. 5,910,491 and others. The final product is formed via a modified Minisci alkylation—i.e., taking camptothecin and reacting it with the Scheme 1 intermediate in the presence of a metal sulfate, with slow addition of sulfuric acid and a strong oxidizing agent (hydrogen peroxide is most preferred) to form the germanium-substituted camptothecin as shown.
[0071] In the structures shown in Scheme 2 (above) and below, ‘X’ refers to a hydrocarbon bridge (alkylene, alkenylene, or alkynylene) of from 1 to 6 total carbon atoms, or it may be a bond if a direct bond of germanium to the scaffold is desired. By varying the hydrocarbon chain length of the intermediate used, the exact length of ‘X’ may also be varied. Substitutions at other positions along the camptothecin scaffold may be added before or after the addition of the germanium side chain.
[0000]
[0072] Scheme 3 illustrates the synthetic process of making a germanium-containing camptothecin where the “E′ ring” is 7- or 8-membered, as opposed to the more naturally-occurring 6-membered ring. The process is the same as that utilized in Scheme 2, with a change in the initial reactants. In this Scheme, X 1 is —CH 2 — or CH 2 CH 2 —.
[0000]
[0073] Scheme 4 illustrates the synthetic process used to make the most preferred molecule of the present invention: 7-[2′-trimethylgermanyl]ethyl-20(S) camptothecin. In this scheme, R 7 , R 8 , and R 9 are all methyl.
[0074] The following examples are illustrative of the synthetic process used to make the Formula (I) compounds and intermediates, and are not limitative of the present invention.
EXAMPLE 1
Preparation of (2-[1,3]Dioxolan-2-yl-ethyl)-trimethyl germanium
[0075]
[0076] To a suspension of magnesium (0.37 g, 15.2 mmol) in tetrahydrofuran (THF) (10 mL) was added 2-(2-bromoethyl)-1,3-dioxolane (2.7 g, 13.9 mmol) at 0° C. The mixture was warmed to room temperature. After the reaction was initiated, the reaction mixture was brought back to 0-5° C. The reaction was then continued for 2 hours at 0° C. and 16 hours at room temperature. The reaction was subsequently quenched with 10 ml of ice water, extracted 3-times with 10 ml of ether and concentrated. The crude product was bulb-to-bulb distilled in a Kugelrohr apparatus to give the title product, (2-[1,3]Dioxolan-2-yl-ethyl)-trimethyl germanium, as clear oil.
[0077] 1 H NMR (300 MHz, CDCl 3 ) δ 4.76 (1H, t), 3.77-3.95 (4H, m), 1.57-1.65 (2H, m), 0.67-0.75 (2H, m), 0.058 (9H, s).
[0078] 13 C NMR (300 MHz, CDCl 3 ) δ 106.3, 65.1, 29.6, 10.4, −2.38.
EXAMPLE 2
Preparation of 7-[2′-trimethylgermanyl]ethyl-20(S) camptothecin (BNP1394)
[0079]
[0080] To a suspension of camptothecin (200 mg) in water (10 mL) and acetic acid (5 mL) was added FeSO 4 .7H 2 O (400 mg). The mixture was stirred for 10 min at room temperature. (2-[1,3]Dioxolan-2-yl-ethyl)-trimethyl-germanium (0.5 ml) was added and the resultant mixture was then cooled to 0° C. Concentrated H 2 SO 4 was added dropwise followed by 30% H 2 O 2 (0.3 ml). The solution was stirred at room temperature for 3 hours and the reaction was poured into ice. The aqueous phase was then extracted 3-times with 20 mL of chloroform. The combined organic extracts were washed with water, dried over anhydrous sodium sulfate, filtrated through silica gel, and concentrated by rotary evaporation. Purification by column chromatography over silica gel (50% ethyl acetate/hexanes as eluents) provided 7-[2′-trimethylgermanyl]ethyl-20(S) camptothecin (designated as BNP1394; 50 mg) as a yellow solid.
[0081] 1 H NMR (300 MHz, CDCl 3 ) δ 8.18 (dd, 1H, J 1 =8.4 Hz, J 2 =0.9 Hz), 7.99 (d, 1H, J=7.5 Hz), 7.77-7.70 (m, 1H), 7.63-7.58 (m, 2H), 5.69 (d, 1H, J=16.5 Hz), 5.25 (d, 1H, J=16.2 Hz), 5.19 (s, 2H), 3.70 (s, 1H), 3.12-3.06 (m, 2H,), 1.89-1.54 (m, 2H), 1.06-0.96 (m, 5H), 0.24 (s, 9H);
[0082] 13 C NMR (300 MHz, CDCl 3 ) δ 174.2, 157.9, 150.3, 149.7, 147.3, 147.0, 130.9, 130.2, 127.8, 126.8, 126.3, 123.5, 118.6, 98.2, 72.9, 66.7, 49.5, 31.8, 25.4, 17.5, 8.00, −2.26 ppm
[0083] MS (ESI) m/z 492 (M+1, 58%), 494 (M+3, 74%), 496 (M+5, 100%).
[0084] Cytotoxicity Results: Comparison of BNP1394 to BNP1350 and Other Camptothecins
[0085] Wild type human ovarian cancer cells (A2780/WT) and doxorubicin-resistant human ovarian cancer cells (A2780/DX5) were cultured in RPMI 1640 medium supplemented with 10% fetal bovine serum and 2 mM glutamine, and grown in a 37° C. incubator with 5% CO 2 . BNP1350 (also designated 7-[2-trimethylsilyl)ethyl]-20(S)-camptothecin; BNP1350; and Karenitecin®); BNP1394 (also designated 7-[2′-trimethylgermanyl]ethyl-20(S) camptothecin; Topotecan; and 9-NH 2 -camptothecin were synthesized and purified at BioNumerik Pharmaceuticals, Inc., and dissolved in DMSO for use in cytotoxicity experiments where inhibition of cell growth was measured using the sulforhodamine B (SRB) assay to assess cytotoxicity and absorbance at 570 nm (A 570 ) in order to calculate the percentage of cell control (or percent cell survival) SRB assay. See. e.g., Skehan P., Stieng R., Scudiero D., et al. New colorimetric cytotoxicity assay for anticancer-drug screen. J. Natl. Cancer Inst. 82:1107-1112 (1990)).
Reagents
[0086] Roswell Park Memorial Institute (RPMI 1640) medium, fetal bovine serum (FBS), and L-glutamine were purchased from Gibco BRL. Drugs were dissolved in sterile dimethylsulfoxide (DMSO), from American Type Culture Collection (ATCC) for stock solutions (2.5 to 5.0 mM). Subsequent dilutions were made using cell culture medium (prior to adding the drug to cells). SRB was purchased from Sigma and dissolved in 1.0 percent acetic acid. Trichloroacetic acid was purchased from VWR International.
Instrumentation
[0087] Cells were manipulated in a Class IIA/B3 Biological Safety Cabinet (Forma Scientific) and maintained at 37° C. in a humidified atmosphere containing 5% CO 2 in a water-jacketed cell culture incubator (Forma Scientific). Cells were counted using a Coulter-Z1 counter (Beckman-Coulter). Following drug treatment, plates were washed using a Biomek 2000 station (Beckman) and, following exposure to SRB dye, plates were washed using an automated plate washer (Model EL404, Bio-Tek Instruments). Percentage of control was correlated to A 570 values and determined using a Model EL800 plate reader (Bio-Tek Instruments).
Cell Growth and Viability
[0088] Briefly, cells were seeded (500 cells/well in 100 μL volume) to 96-well microliter plates and allowed to attach for 24 hours prior to treatment with BNP1350, BNP1394, Topotecan, and 9-NH 2 -camptothecin for 2 hours. Following this 2 hour treatment, BNP1350, BNP1394, Topotecan, and 9-NH 2 -camptothecin were removed, cells were washed with drug-free media (200 μL) and then drug-free media (200 μL) was added to the cells and cells were allowed to continue growing at 37° C. with 5% CO 2 before the SRB assay was performed (total experiment time from time of seeding was 5 days, during which a total of five (5) cell-doublings occurred).
Cell Growth and Viability
[0089] Wild-type human ovarian cancer cells (A2780/WT) and doxorubicin-resistant human ovarian cancer cells (A2780/DX5) were cultured in RPMI 1640 medium supplemented with 10% fetal bovine serum and 2 mM L-glutamine, and grown in a 37° C. incubator with 5% CO 2 . Population doubling times for the two cell lines used in this study encompassed a total of five cell doublings corresponding to approximately 5 days for A2780/WT and A2780/DX5 cells. Both cell lines were maintained as monolayered cultures in T-25 or T-75 flasks and then seeded to microliter plate wells for experiments described herein.
[0090] In brief, cells were seeded (500 cells/well in 100 μL total volume) into 96-well microliter plates and allowed to attach for 24 hours prior to treatment with BNP1350, BNP1394, Topotecan, or 9-NH 2 -camptothecin for 2 hours. The aforementioned compounds were dissolved in DMSO for use in cytotoxicity experiments where inhibition of cell growth was measured using the SRB assay.
[0091] Following this 2 hour drug treatment, the BNP1350, BNP1394, Topotecan, and 9-NH 2 -camptothecin were removed, cells were washed with drug-free media (200 μL) and then drug-free media (200 μL) was added to the cells and cells were allowed to continue growing at 37° C. with 5% CO 2 before the SRB assay was performed (total experiment time from time of seeding was 5 days, during which time a total of 5 cell doublings had occurred).
[0092] Prior to SRB assays, cell viability was monitored by evaluation of microliter plate wells. Dead cells detach and float while living cells remain attached to the bottom of the cell well.
Cytotoxicity Assay (SRB Assay)
[0093] The sulforhodamine B (SRB) cytotoxicity assay (see, Skehan P, et al., New colorimetric cytotoxicity assay for anticancer-drug screening. J. Natl. Cancer Inst. 82:1107-1112 (1990)) was used to determine the cytotoxic effects of BNP1350, BNP10120 or BNP10121 on cell growth in vitro. Briefly, after the medium was aspirated from individual plate wells, trichloroacetic acid (100 μL of 10.0% solution) was added to each well, and the plates were incubated at 4° C. for at least 1 hour. The plates were washed five-times with water using an automated microplate washer (Model EL 404, Bio-Tek Instruments), SRB solution (100 μL of 0.4 grams SRB dissolved in 100 mL 1.0 percent acetic acid) was added, and plates remained at room temperature for 15 minutes. The plates were then washed five-times using acetic acid (1.0%), air dried, and bound dye was solubilized in Tris base (150 μL, 10 mM). Plates were agitated (gently) for 5 minutes and the absorbance values of the SRB dye-protein adduct at a 570 nm wavelength (A 570 ) were determined using an automated microtiter plate reader equipped with an A 570 filter (Model EL800, BioTek Instruments).
Experimental Results
[0094] BNP1350, BNP1394, Topotecan, and 9-NH 2 -camptothecin were all inhibitors of A2780/WT and A2780/DX5 cell growth. However, BNP1350 and BNP1394 had nanomolar IC50 values and were much more potent than Topotecan or 9-NH 2 -camptothecin, with nanomolar IC50 values (see, Table 1; Graph 1).
[0000]
TABLE 1
Summary of IC50 Determinations in Human Ovarian Cancer Cells
Test
Test
Test
Test
Test
Test
Aver-
1
2
3
4
5
6
age
StDev
IC50 (nM)
A2780/WT
BNP1350
15
15
15
20
13
16
15
3
BNP1394
20
15
9
20
18
18
17
4
9-NH 2 -
150
90
150
200
250
90
155
63
camptothecin
Topotecan
350
200
300
600
900
600
492
258
IC50 (nM)
A2780/DX5
BNP1350
15
15
15
24
10
n/a
16
5
BNP1394
25
15
9
25
15
25
19
7
9-NH 2 -
600
250
250
550
600
n/a
450
184
camptothecin
Topotecan
550
800
2000
1000
2000
n/a
1270
685
SPECIFIC EXAMPLES OF FORMULATIONS OF THE PRESENT INVENTION
[0095] In its preferred embodiments, the present invention involves the preparation and administration of germanium-containing camptothecin formulations. The following examples of the administration of these formulations illustrate selected modes for carrying out the present invention, and are not to be construed as limiting in any way.
Example I
[0096] For injection or infusion into aqueous body fluids, a formulation comprises a total dose of from approximately 0.1 mg/m 2 to approximately 100 mg/m 2 of the germanium-containing camptothecin dissolved in 1 to 10 parts of N-methylpyrrolidinone, dimethylisosorbide and/or dimethylacetamide in an acidified vehicle comprising between approximately 10 to approximately 40 percent of an acceptable alcohol, approximately 4 to approximately 10 parts by weight of polyether glycol, and approximately 1 to approximately 10 parts of a non-ionic surfactant. Suitable alcohols include dehydrated ethyl alcohol, benzyl alcohol. Suitable polyether glycols, include polyethylene glycol 200, polyethylene glycol 300, propylene glycol. Suitable non-ionic surfactants include, but are not limited to, polysorbate-80. In a preferred embodiment, the formulation of the germanium-containing camptothecin is supplied as an intravenous injectable in a 1 mg vial comprising a sterile, nonaqueous solution of drug in a vehicle comprising dehydrated ethyl alcohol, benzyl alcohol, citric acid, polyethylene glycol 300, and polysorbate (Tween 80) in acidified medium with a pH of 3 to 4 at a final concentration of 1 mg per 1 to 2 mL
Example II
[0097] A second formulation comprises a total dose of from approximately 0.1 mg/m 2 to approximately 100 mg/m 2 of the germanium-containing camptothecin in an acidified vehicle comprising between approximately 0.1 to 2 parts of an alcohol and approximately 1 to 10 parts of a non-ionic surfactant. Suitable alcohols include dehydrated ethyl alcohol USP, and benzyl alcohol. Suitable non-ionic surfactants include the polyoxyethylated oils, such as polyoxyethylated vegetable oils, such as castor oil, peanut oil, and olive oil. In a preferred embodiment 1 mg to 200 mg the germanium-containing camptothecin is formulated in 1 to 10 parts of N-methylpyrrolidinone, dimethylisosorbide and/or dimethylacetamide, 1 to 10 parts of Cremaphor EL™ (polyoxyethylated castor oil), 0.1 to 2 parts by weight dehydrated ethyl alcohol USP, and 0.1 to 0.9 parts citric acid to adjust the final pH between 3 to 4.
Example III
[0098] An oral formulation of the germanium-containing camptothecin in soft gelatin capsules (e.g., comprised of gelatin/glycerin/sorbitol/purifiers) containing 1.0 part of the germanium-containing camptothecin in 1 to 10 parts of N-methylpyrrolidinone, dimethylisosorbide and/or dimethylacetamide, citric acid 0.1 to 0.5 parts by weight, glycerin 1 to 10 parts by weight, and polyethylene glycol 200 to 300 5 to 9 parts by weight, dehydrated ethyl alcohol 0.2 to 2 parts by weight of total solution weight, sodium acetate 0.05 to 0.5 parts by weight, pluronic poloxamer using 0.05 to 1.0 parts by weight, and taurocholic acid 2 to 10 parts by weight. The soft gelatin capsules may also be composed of any of a number of compounds used for this purpose including, for example, a mixture of gelatin, glycerin, sorbitol, and parabens.
[0099] It should be noted that in order to prolong the stability and solubility of the germanium-containing camptothecin for clinical infusions, the drug may diluted in 5% Dextrose in water (D5W) to a final concentration so as to provide a total dose of approximately 0.1 mg/m 2 to approximately 100 mg/m 2 of the germanium-containing camptothecin prior to injection or infusion.
[0100] Maintaining an acidic pH (i.e., pH 3 to 4) in the formulation is particularly important to reduce the slow conversion of the germanium-containing camptothecin (i.e., active form) to the E-ring-hydrolyzed carboxylate (i.e., inactive form), which occurs at physiological pH. At equilibrium under physiologic pH, the ratio of the inactive, “open-ring” form to lactone increases. Hence, hydrolysis of the lactone ring will be substantially reduced if the drug is kept in an acidic environment. The lactone form of, e.g., naturally-occurring camptothecin, as in the germanium-containing camptothecin of the present invention, is less water soluble than the carboxylate E-ring form. As previously discussed, when early clinical trials were first conducted with camptothecin using NaOH, the significance of maintaining the closed lactone ring for uniform efficacy in treating patients with cancer was poorly understood. The early reported unpredictable clinical toxicities associated with camptothecin administration may have been exacerbated by the NaOH formulation which promotes the formation of the carboxylate form, and by the relative lack of understanding of the significance of the lactone form of camptothecin as it relates to chemotherapeutic activity.
Specific Examples of the Administration of Formulations
[0101] The foregoing description of the formulation invention has been directed to particular preferred embodiments in accordance with the requirements of the patent statutes and for purposes of explanation and illustration. Those skilled in the art will recognize that many modifications and changes may be made without departing from the scope and the spirit of the invention.
[0102] The administration of the germanium-containing camptothecin of the present invention may be carried out using various schedules and dosages. For example:
(1) For intravenous administration, a suitable dose is approximately 0.1 mg/m 2 to approximately 100 mg/m 2 in a 24 hour period which can be administered in a single or divided into multiple doses, depending upon the attending physician. This dosing regiment may be repeated for 48 hours or more. Other suitable intravenous dosing schedules range from approximately 0.1 mg/m 2 to approximately 100 mg/m 2 per day using a 3 to 5 day continuous infusion schedule every 21 to 30 days and approximately 0.1 mg/m 2 to approximately 100 mg/m 2 given as a 30 to 90 minute infusion every 21 to 30 days. (2) A suitable oral dose of the drug is approximately 0.1 mg/m 2 to approximately 100 mg/m 2 per day using the lower dose for a period of 3 to 5 days and using divided dosages of administration of two to four times per day. Other suitable oral dosing schedules range from approximately 0.1 mg/m 2 to approximately 75 mg/m 2 per day for a period of 3 to 5 days and approximately 0.1 mg/m 2 to approximately 50 mg/m 2 per day for a period of 3 to 5 days.
[0105] It should be noted that the parenteral and oral doses can be administered under the supervision of a physician based on gradual escalation of the dosage to achieve the maximum tolerated dose in the individual patient. The oral administration schedule of the germanium-containing camptothecin may involve multiple daily doses or single daily doses for one or more consecutive days with the ability of the physician to optimize therapy by reaching the maximum effective chemotherapeutic dose that has the least toxicity in the individual patient.
[0106] In addition, patients may be given the germanium-containing camptothecin of the present invention as either an inpatient or outpatient, using the following exemplary schedules:
(1) approximately 0.1 mg/m 2 to approximately 100 mg/m 2 given over 90 minutes I.V. every 21 to 28 days; (2) approximately 0.1 mg/m 2 to approximately 100 mg/m 2 given daily for three consecutive days over 90 minutes I.V. every 21 to 28 days; (3) approximately 0.1 mg/m 2 to approximately 100 mg/m 2 week given once per week×3 consecutive weeks over 90 minutes I.V. with 2 weeks rest after each 3 week cycle for pretreated patients; (4) approximately 0.1 mg/m 2 to approximately 100 mg/m 2 given once per week×3 consecutive weeks over 90 minutes I.V. for previously untreated patients with 2 weeks rest after each 3 week cycle; and (5) approximately 0.1 mg/m 2 /d to approximately 100 mg/m 2 /d×3-5 consecutive days as a continuous i.v. infusion every 21 to 28 days.
[0112] In a preferred embodiment, the germanium-containing camptothecin is initially given at a lower dose. The dose of the germanium-containing camptothecin is then escalated at each successive cycle of treatment until the patient develops side effects which demonstrates the individual's therapeutic tolerance. The purpose of dose escalation is to safely increase the drug levels to a maximum tolerated dose and should result in increased cytotoxicity and improved chemotherapeutic activity.
[0113] Dosages can be escalated based on patient tolerance as long as unacceptable toxicity is not observed. “Unacceptable toxicity” is defined by World Health Organization (WHO) as grade 3 non-hematologic toxicity excluding nausea and vomiting and grade 4 vomiting or hematologic toxicity according to the National Cancer Institute common toxicity criteria. Since some clinical 2 5 drug toxicity is anticipated in routine clinical oncology practice, appropriate treatment will be used to prevent toxicity (e.g., nausea and vomiting) or ameliorate signs and symptoms if they are observed (e.g., diarrhea). For example, antiemetics will be administered for nausea and vomiting, antidiarrheals for diarrhea, and antipyretics for fever. Appropriate dosages of steroids/antihistamines will also be used to prevent or ameliorate any anaphylactoid toxicity if an anaphylactoid reaction is observed.
Determination of Serum Levels
[0114] Kaneda's HPLC method and further modifications by Barilero, et al., (Simultaneous Determination of the Camptothecin Analogue CPT-11 and Its Active Metabolite HECPT by High Performance Liquid Chromatography: Application to Plasma Pharmacokinetic Studies in Cancer Patients. J. Chromat. 575:275-280 (1992)) are useful for the measuring quantities of various camptothecins (including the germanium-containing camptothecin of the present invention) in plasma and tissue.
[0115] All patents, publications, scientific articles, web sites, and other documents and materials referenced or mentioned herein are indicative of the levels of skill of those skilled in the art to which the invention pertains, and each such referenced document and material is hereby incorporated by reference to the same extent as if it had been incorporated by reference in its entirety individually or set forth herein in its entirety. Applicants reserve the right to physically incorporate into this specification any and all materials and information from any such patents, publications, scientific articles, web sites, electronically available information, and other referenced materials or documents.
[0116] The written description portion of this patent includes all claims. Furthermore, all claims, including all original claims as well as all claims from any and all priority documents, are hereby incorporated by reference in their entirety into the written description portion of the specification, and Applicants reserve the right to physically incorporate into the written description or any other portion of the application, any and all such claims. Thus, for example, under no circumstances may the patent be interpreted as allegedly not providing a written description for a claim on the assertion that the precise wording of the claim is not set forth in haec verba in written description portion of the patent.
[0117] The claims will be interpreted according to law. However, and notwithstanding the alleged or perceived ease or difficulty of interpreting any claim or portion thereof, under no circumstances may any adjustment or amendment of a claim or any portion thereof during prosecution of the application or applications leading to this patent be interpreted as having forfeited any right to any and all equivalents thereof that do not form a part of the prior art.
[0118] All of the features disclosed in this specification may be combined in any combination. Thus, unless expressly stated otherwise, each feature disclosed is only an example of a generic series of equivalent or similar features.
[0119] It is to be understood that while the invention has been described in conjunction with the detailed description thereof, the foregoing description is intended to illustrate and not limit the scope of the invention, which is defined by the scope of the appended claims. Thus, from the foregoing, it will be appreciated that, although specific embodiments of the invention have been described herein for the purpose of illustration, various modifications may be made without deviating from the spirit and scope of the invention. Other aspects, advantages, and modifications are within the scope of the following claims and the present invention is not limited except as by the appended claims.
[0120] The specific methods and compositions described herein are representative of preferred embodiments and are exemplary and not intended as limitations on the scope of the invention. Other objects, aspects, and embodiments will occur to those skilled in the art upon consideration of this specification, and are encompassed within the spirit of the invention as defined by the scope of the claims. It will be readily apparent to one skilled in the art that varying substitutions and modifications may be made to the invention disclosed herein without departing from the scope and spirit of the invention. The invention illustratively described herein suitably may be practiced in the absence of any element or elements, or limitation or limitations, which is not specifically disclosed herein as essential. Thus, for example, in each instance herein, in embodiments or examples of the present invention, the terms “comprising”, “including”, “containing”, etc. are to be read expansively and without limitation. The methods and processes illustratively described herein suitably may be practiced in differing orders of steps, and that they are not necessarily restricted to the orders of steps indicated herein or in the claims.
[0121] The terms and expressions that have been employed are used as terms of description and not of limitation, and there is no intent in the use of such terms and expressions to exclude any equivalent of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention as claimed. Thus, it will be understood that although the present invention has been specifically disclosed by various embodiments and/or preferred embodiments and optional features, any and all modifications and variations of the concepts herein disclosed that may be resorted to by those skilled in the art are considered to be within the scope of this invention as defined by the appended claims.
[0122] The present invention has been described broadly and generically herein. Each of the narrower species and subgeneric groupings falling within the generic disclosure also form part of the invention. This includes the generic description of the invention with a proviso or negative limitation removing any subject matter from the genus, regardless of whether or not the excised material is specifically recited herein.
[0123] It is also to be understood that as used herein and in the appended claims, the singular forms “a,” “an,” and “the” include plural reference unless the context clearly dictates otherwise, the term “X and/or Y” means “X” or “Y” or both “X” and “Y”, and the letter “s” following a noun designates both the plural and singular forms of that noun. In addition, where features or aspects of the invention are described in terms of Markush groups, it is intended, and those skilled in the art will recognize, that the invention embraces and is also thereby described in terms of any individual member and any subgroup of members of the Markush group, and applicants reserve the right to revise the application or claims to refer specifically to any individual member or any subgroup of members of the Markush group.
[0124] Other embodiments are within the following claims. The patent may not be interpreted to 2 0 be limited to the specific examples or embodiments or methods specifically and/or expressly disclosed herein. Under no circumstances may the patent be interpreted to be limited by any statement made by any Examiner or any other official or employee of the Patent and Trademark Office unless such statement is specifically and without qualification or reservation expressly adopted in a responsive writing by Applicants. | The present invention discloses: (i) the novel germanium-containing camptothecin compound, 7[2′-trimethylgermanyl]ethyl-20(S) camptothecin, and pharmaceutically-acceptable salts thereof; (ii) methods of synthesis of said novel germanium-containing camptothecin compound, 7[2′-trimethylgermanyl]ethyl-20(S) camptothecin, and pharmaceutically-acceptable salts; (iii) pharmaceutically-acceptable formulations comprising said novel germanium-containing camptothecin compound, 7[2′-trimethylgermanyl]ethyl-20(S) camptothecin, and pharmaceutically-acceptable salts thereof; and (iv) methods of administration of said novel germanium-containing camptothecin compound, 7[2′-trimethylgermanyl]ethyl-20(S) camptothecin, and pharmaceutically-acceptable salts thereof to subjects in need thereof, including subjects with cancer. | 2 |
FIELD OF THE INVENTION
This invention relates generally to a thermal cycling device and, more specifically, to an apparatus for the rapid heating and cooling of liquid samples.
BACKGROUND OF THE INVENTION
A thermal cycling device is an apparatus used to continuously change the temperature of a liquid sample. As used herein, the term “liquid” refers to pure liquids, as well as liquids containing particulate matter (especially biological material) and solvents containing solute.
Thermal cycling devices are well-known in the art and specific embodiments have been described in the scientific and patent literature. These devices fall into two general categories.
The first category is a system based on the heating or cooling of a metal block typically either by moving a fluid through the block or by the addition of peltier heating directly to the block. A number of individual plastic tubes, a well plate (or a microliter plate which consists, essentially, of a number of plastic tubes connected together in a rectangular array) are used to hold the liquid samples. The plastic tubes are placed in the block and the temperature of the sample is regulated by changing the temperature of the metal block. The rate at which the temperature can be changed is limited by the relatively large thermal mass of the metal block. This being the case, the maximal rate of temperature change is relatively slow due to the fact that heat has to be added or removed from a relatively large thermal mass and this mass takes a significant time to reach thermal equilibrium. A second disadvantage of this category of thermal cyclers is that the liquid samples to be heated or cooled are “insulated” from the block by the plastic wall of the sample container (i.e., by the plastic tubes). Since plastic is a good insulator, not only must the heating and cooling source overcome the thermal mass of the metal block, but it must also overcome the insulating properties of the plastic sample container.
The sample containers currently in use for polymerase chain reaction (PCR) and Cycle Sequencing are either thin walled microfuge tubes, thin walled microwell plates—usually either 96-well or 384-well—or microcapillary tubes. All of these containers suffer from a common problem in that in all cases, the samples are heated or cooled from an external source and the heating and cooling system must overcome the insulating properties of the container.
A related problem with these devices is that the plastic tubes are quite large in comparison to the liquid sample. For example, when a 96-well plate or 384-well plate is used in these systems, the container volume ranges from 300 microliters (μl) to 120 μl whereas the sample volume is usually only 5-25 μl. When a sample is heated during a polymerase chain reaction (PCR) cycle, the liquid will evaporate and condense on the interior wall surfaces of the sample container. Loss of liquid from the sample will change the concentrations of the reaction components and lead to spurious results.
Specific measures have been taken to overcome the serious problem of evaporation and condensation. One solution is to place a lid over the sample container or well plate. A heated well-plate is placed in contact with the sample container lid and heated to 20-30° C. higher than the sample temperature. This will minimize the condensation of the liquid on the walls and surface of the container but does nothing for the total evaporation since the air volume within the sample container is large and can hold a significant amount of liquid vapor (from 0.06-0.15 μl), especially at these elevated temperatures. In a 25 μl reaction volume, this liquid loss may not have a significant effect, however, when the reaction volume approaches 1 μl, a loss of 15% of the liquid volume will adversely affect the reaction.
A number of manufacturers currently produce thermal cyclers that utilize a metal block for heating and cooling liquid samples. These include MJ Research, Techne, Lab Line, Thermolyne, Corbett Research, and Hybaid.
The second type of thermal cycling device involves the use of microcapillary tubes that are placed in a chamber, and heating the chamber by forcing hot air or cold air into the chamber. This method is somewhat similar to heating the samples with a convection oven and cooling the samples with a refrigeration system. A current manufacturer of this type of thermal cycler is Idaho Technologies.
This second type of thermal cycling device has the advantage that the thermal mass that needs to be heated is relatively small, i.e, the capillary tube, sample, and the interior of the chamber. However, this system has a number of limitations. First, the samples need to be sealed within a glass capillary tube. This requires that the sample be drawn into the tube via capillary action then the end of the tube has to be sealed with a flame hot enough to melt the glass. Capillary tubes by their very nature are difficult to manipulate and are not suitable to robotic automation. That is, while a limited number of samples can be prepared in this fashion, it would be extremely difficult, if not impossible to process the number of samples per day (usually on the order of 100,000 that are usually necessary for a particular study). Second, glass is a fairly good insulator so, similar to the problem described above with the plastic tubes, this system is also limited in that in order to heat or cool the sample, the insulating properties of the container must be overcome.
One of the biggest drawbacks of the commonly used polypropylene microwell plates is that the material changes shape upon repeated heating and cooling cycles. For example, upon heating a standard polypropylene microwell plate to 95° C. and cooling back to room temperature, the plastic may deform by as much as 1 cm from corner to corner. The result of this is that the plate cannot be used directly on standard laboratory automation—for example, a 96 or 384 channel pipettor would hit the bottom of the wells on one corner of the plate yet remain up to 1 cm from the bottom of the other corner of the plate. To compensate for this, the samples are typically moved, singly, into a plate that has not been subjected to thermal cycling or the plate is forced into a retaining device that will hold the plate in the proper shape.
Microcapillaries as a container for PCR and Cycle Sequencing have an associated set of problems. First and foremost is the fact that these containers are not automation friendly. That is, it is difficult if not impossible for robotic liquid handlers to place liquid within a capillary. Consequently, the liquid handling is typically performed in a microfuge tube or microwell plate; then the capillary is brought into contact with the liquid and the liquid is drawn into the capillary by capillary action. This negates one of the presumed advantages of the capillary system in that a significantly larger volume of reagent must be prepared even though only a small portion of that reagent is used within the capillary. Another problem with capillaries is that they are difficult to seal. Each capillary typically has to be heat sealed to melt the glass capillary. Even if other types of materials are used for the capillaries, sealing is difficult and not amenable to automation. Finally, after the reaction has taken place, the capillary must be broken or cut and the reaction product removed. Since the sample is held within the capillary by capillary action, the removal of the sample is difficult at best.
In order to increase throughput and decrease the volume of the reaction, there is a desire to move from 384-well plates to 1536-well plates. This will allow a four-fold increase in density and throughput and, because the volume of the well is much smaller (75 microliters in a 384-well plate vs. − 6 microliters in a 1536 well plate) the reactions can be performed at 1 microliter vs. the typical 5-25 microliters that is currently performed in 384-well plates. The miniaturization from a 384-well system to a 1536-well system will yield about a 5-25 fold reagent savings. These two advancements over the current methods will yield nearly a 100-fold improvement in reagent savings and throughput.
Commercially available 1536-well plates are not conducive to the current methods of thermal cycling. There are several reasons for this. With a very high well density and a center to center spacing of 2.25 millimeters the inter-well distance is approximately 0.5 millimeters. This small distance makes it nearly impossible to surround each well with a heating/cooling unit as is currently done in 96-well or 384-well systems. Also, the plastic surface area to volume ratio is approximately 7-fold higher than in a 96-well plate or 384-well plate. With the increased plastic area, the insulating properties of the plastic that comprises the well is very difficult to overcome. Heating the plate from just the bottom is not practical since this causes temperature gradients within the well and consequently non-uniform heating.
Typically, PCR and other methods have involved placing the samples in a small microtube and then placing the microtube in a water bath or heat block for temperature regulation. This method of controlling the temperature of the reaction has been successfully used on single tubes, 96-well plates, and 384-well plates. However, as the well density increases, it becomes difficult to surround each well with uniform temperature control. Moreover, plastics typically act as excellent insulators so the external heating and cooling system has to overcome the insulating properties of the plastic before an effect on the solution is observed. An additional problem is that the solution volume is very small in comparison to the total well volume. Consequently, when the well is heated, the solution tends to evaporate and then condense on the cover of the well. This causes the concentration of the various components in the well to change and can adversely affect the reaction. To compensate for this problem, many systems heat the covers so that condensation on this surface is limited. An additional problem is that as the well density increases from 96-well plates to 384-well plates, the plates tend to warp and become misshapen during the heating and cooling cycles. This warping of the plates makes it difficult for them to be handled effectively by robotic or automated systems—an absolute requirement for high throughput.
SUMMARY OF THE INVENTION
The present invention can be divided into two embodiments. The first embodiment consists of a device for heating and cooling a lid that is designed to fit over a well plate. There are two variations for this lid heating/cooling system. First, one air source passing over a heating coil and another air source passing over a cooling unit (air conditioning) are proportionally mixed in order to regulate the temperature. The mixed air is directed via a series of ducts such that it heats or cools the surface of the lid in a uniform and highly controlled fashion. The second method is to bring a heating/cooling source, such as a Peltier device or heat/cold block in direct contact with the surface of the lid. The large thermal mass of the heat/cold block will rapidly add or remove heat from the samples via the pins inserted into the sample.
The second embodiment is a device, in particular a well-plate containing, for example, 1536-wells with each well having a volume of approximately 6 μl, and a mating plate lid. The lid to this plate may have a copper clad surface and may contain a rubber seal on the other surface. Protruding through this lid is a series of “pins” that extend approximately from the rubber surface and which communicate with the copper clad surface for transferring heat from the lid. The device in the first embodiment heats or cools the copper clad surface and pins of the device in the second embodiment. The copper clad surface and pins rapidly transfers heat or removes heat from the pins. The pins in turn transfer heat or remove heat from the sample.
The present invention describes a device whereby the wells of a 1536-well plate, for example, can be uniformly heated by applying a heating or cooling source directly into the well via the lid; the pins are either in direct contact with the liquid sample(s) or near the liquid sample(s) such that it can conduct heat into or out of the sample.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are incorporated in and form a part of the specification, illustrate the embodiments of the present invention and, together with the description, serve to explain the principles of the invention.
FIG. 1 illustrates a lid having a copper clad surface on one side in accordance with the present invention.
FIG. 2A illustrates a lid, in accordance with the present invention, having a copper silicone rubber layer applied to the bottom surface and pins through the lid.
FIG. 2B is an enlarged view of the lid illustrated in FIG. 2 A.
FIG. 3 is a side view similar to FIG. 2 illustrating the position of the lid with pins with respect to the well-plate.
FIG. 4 is a hole positioning on the lid for insertion of the 32 by 48 pin array and locators for the plate positioning component.
FIG. 5 illustrates a compression fitting of the pin such that it is firmly seated in the hole in the lid and in direct contact with the copper clad surface.
FIG. 6 is a perspective view of a plate positioning component and its role in protecting the pin array from damage.
FIG. 7 is a perspective view of a means that can apply heat or remove heat from the lids.
FIG. 8 is a portion of a well plate 100 having a well grid of 16 by 24 wells.
FIG. 9 is a portion of a well plate 101 having a well grid of 8 by 12 wells.
FIG. 10 is a pin 18 mounted on lid 10 having a coating 20 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
In describing a preferred embodiment of the invention, specific terminology will be selected for the sake of clarity. However, the invention is not intended to be limited to the specific terms so selected, and it is to be understood that each specific term includes all technical equivalents that operate in a similar manner to accomplish a similar purpose.
Referring to FIG. 1, the subject invention consists of a lid 10 that transmits heat to liquid samples 95 that are stored in a well-plate 99 . In a preferred embodiment, a means for regulating the temperature of the lid 10 may be included with the heat-transmitting lid.
The lid 10 must be able to conduct heat. In a first preferred embodiment, the lid 10 is constructed from a circuit board type material, which gives the lid rigidity. A circuit board is typically made of a polymer base 12 and may have a copper clad layer 14 as illustrated in FIG. 1 . In actuality, the clad layer may be any suitable metal and, preferably, is a material that conducts heat.
The lid 10 is preferably adapted to be frictionally or matingly fitted over a well-plate 99 . A means for heating and cooling the lid is applied to the lid 10 . The close proximity of the lid 10 to the liquid samples 95 in the well-plate 99 controls the temperature of the liquid samples. This embodiment is the most basic embodiment in accordance with the present invention. If the lid has a cooper clad surface it is on the “top” side of the lid, away from the liquid samples. The cooper clad surface will distribute the heat more evenly over the lid 10 but is not crucial to this embodiment.
Referring now to FIGS. 2A, 2 B and 3 , a second primary embodiment is illustrated. The base 12 of the lid 10 has a copper clad upper or top layer 14 . As discussed before, the copper clad layer 14 is useful in evenly distributing heat across the entire upper surface of the lid 10 . The side opposite of the copper clad may be coated with a thin layer of silicone rubber 16 or a similar material. The silicone rubber coating 16 helps to seal the lid onto the well-plate 99 thereby inhibiting water loss (evaporation) of the solution during the repeated heating and cooling cycles. However, if the lid 10 is designed to frictionally engage the well-plate 99 , only a perimeter coating of silicone rubber or no silicone rubber may be needed.
One or more pins 18 communicate with the copper clad surface of the lid 10 in order to transmit heat from the top of the lid along the length of the pins 18 .
In a preferred embodiment, a plurality of holes, substantially the diameter of the pins 18 that will be used, are drilled into the lid 10 on a dimensional array that corresponds to the dimensions of the well plate 99 that will be used. For example, for a 1536-well plate having a 32 by 48 array of wells, the holes would be drilled in a 32 by 48 array with a center to center spacing of 2.25 millimeters as illustrated in FIG. 4 . The 1536 pins 18 are then inserted through these holes such that they protrude beyond the silicone seal as illustrated in FIGS. 2A, 2 B and 3 . Based on the depth of a standard 1536-well plate, the pins will protrude approximately 3 mm from the bottom surface of the lid 10 .
The pins are compression fit into the lid 10 such that each pin is in direct contact with the copper clad as illustrated in FIG. 5 . In order to achieve this, Knurls may be formed proximate the top of each pin 18 . In addition, a head on each pin 18 may prevent it from sliding completely through the hole. It will be appreciated by those skilled in the art that other means for attaching the pins may be used, for example, soldering the top of each pin to the copper clad surface 14 .
The pins may or may not protrude from the side with the copper clad (i.e., the top side of the lid). If the pins do protrude above the copper clad surface of the lid, it should preferably not exceed 0.2 mm.
The pins can be constructed from any material that is capable of conducting heat. In the preferred embodiment, the pins are constructed from tin/lead coated brass wire. Other materials such as aluminum, gold, copper, or other metals could be used along with certain ceramics and plastics.
A portion of the pin 18 that extends from the bottom side of the lid is designed to make contact with the sample stored in the respective well. (see FIG. 3 ). It would be obvious to one skilled in the art that the pin lengths and the amount of liquid sample may be adjusted to ensure that the pins are at least partially submerged in the liquid sample. Accordingly, as the temperature of the lid is changed, the temperature of the pins change, thereby directly heating or cooling the sample.
An advantage of this system is the volume of the heating/cooling device, “pin”, versus the volume of the sample. In this system, the heating/cooling device that is inserted directly into the sample has a volume of approximately 10% of the liquid volume. This comparatively large volume pin insures rapid temperature equilibrium in the sample. Also, the pin 18 can be designed to maximize surface area such that heat transfer between the liquid sample and the pin is optimized. The larger the pin cross sectional area, the faster the heat transfer.
It would be understood by one skilled in the art that if the pin 18 directly contacts the liquid sample, then the temperature of the sample may be more quickly brought to a desired temperature. However, if the pins are designed so that they do not directly contact the liquid sample, the temperature of the sample will still change because of each sample's proximity to its respective pin 18 .
In some circumstances, the metal pins may need to be coated with a plastic or other inert material so that the metal will not interfere with the reaction that is to occur in the samples. If this is the case, the pins can be coated with gold, polypropylene, polystyrene, or other metals, plastics or ceramics that are biologically inert.
The pins in the preferred embodiment are cylindrical in shape. However, rectangular, hexagonal, elliptical, star or other shaped rods could also be used.
The tip of the pin that protrudes into the liquid can be concave or convex, have ridges or other structures that can trap small quantities of liquid. One advantage of this system is that after the PCR or cycle sequencing reaction is complete, the lid can be removed and used as a storage device for a small amount of the material in the well. If the reaction needs to be repeated the lid can be reused to generate a new sample by the small quantities of the samples attached to the pins. The lid 10 can also be used to place small amounts of sample onto other substrates.
If the lid 10 is clad in metal, then the pins can be heated either by row, column, or individually, simply by cutting the metal clad such that there are two or more separate areas that can be heated or cooled individually. In this case, the thermal cycler could be constructed in the form of a Peltier device such that the Peltier could be brought into direct contact with a row or column of pins.
Referring to FIGS. 2A, 3 and 6 , the lid 10 includes two or more plastic ears 90 that serve several purposes. First, these plastic pieces are used to position the lid on the plate such that the pins are inserted directly into the corresponding well. These plastic ears 90 also serve to protect the pins both from contamination and from potential damage as illustrated in FIG. 6 .
The actual thermal mass that needs to be heated or cooled in this device is very small and includes the thin sheet of copper clad on the surface of the lid and the pin array. This low thermal mass allows the temperature of the system to be changed very rapidly and thermal equilibrium will be reached rapidly.
The 1536-well plate is constructed based on the Proposed Society for Biomolecular Screening (SBS) standard plate configuration. The overall dimensions of the plate are: 85.48 mm in width, 127.76 mm in length, and 14.75 mm in height. The well-to-well spacing on the 1536-well plate is 2.25 mm center to center and on the 384-well plate is 4.5 mm center to center. The plate meets the SBS standard in all aspects except for the positioning slots 80 illustrated in FIG. 4 to accept the PCR lid. On both short sides of the plate, positioning slots are formed such that the lid 10 can be positioned directly upon the plate without the heating/cooling pins contacting the side walls of the wells.
An automated device for positioning the lid over the well-plate by aligning the pins with its corresponding well is easily designed as illustrated in FIG. 7 . As long as the same rectangular array of pins that correspond to the rectangular array of wells is used, a lid 10 can be designed for use with any well-plate.
In a preferred embodiment, the thermal cycler is designed to accept from one to six plates: the plates may have either 96, 384, or 1536 wells. When fully loaded with six 1536-well plates, the system can process >9000 samples at one time.
The thermal cycler tray, onto which the plates will be placed, contains an interlock system that positions each plate precisely in the cycler. This tray indexes out to the user and can be loaded either manually or robotically with plates as illustrated in FIG. 7 . When the tray is moved back into the thermal cycler, a compression screen is brought down into contact with the lid. This compression screen applies a slight pressure to the lid 10 causing it to be compressed onto the plate 99 . This action compresses the rubber seal 16 around each of the wells thus making each well air and liquid tight.
Temperature control within the thermal cycler can be performed by the mixing of two air sources. The first, or “hot”, air source is produced passing air over a resistive heating coil to bring the air temperature up to >250° C. The second, or “cold”, air source is produced by passing air over a refrigeration unit cooling the air to 10° C. These two air sources are then mixed in the proper proportions in the vortex chamber to create air at the proper temperature. Air from the vortex chamber is then passed over the copper clad surface of the lids 10 in the sample chamber. This conditioned air then either heats or cools the copper clad surface 14 and copper pins 18 of the lid 10 . As the pins heat or cool, heat is either added directly to the samples through the pins or removed directly from the samples through the pins and dissipated at the copper clad surface 14 of the lid 10 .
Temperature control can also be achieved by the application of a Peltier device directly to the copper clad surface of the lid. In this case, the heating/cooling system is incorporated directly into the clamping device such that when the lid is clamped onto the plate, the Peltier device is compressed onto the copper clad surface of the lid. The application of current to the Peltier device will then heat one surface of the Peltier device while cooling the other side. Reversing the current flow will reverse the hot and cold surfaces.
As the peltier device heats up, the heat energy is transferred to the copper clad portion of the lid. Similar to the embodiment that uses air to regulate the temperature of the samples, the lid transmits its energy to the pins and eventually to the samples.
Other means of heating and cooling the lid may be used. For example, applying a metal block that has either been heated or cooled to the appropriate temperature may be used to regulate the temperature of the lid 10 and ultimately the liquid samples.
Although this invention has been described and illustrated by reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications may be made which clearly fall within the scope of this invention. The present invention is intended to be protected broadly within the spirit and scope of the appended claims.
FIG. 8 shows a portion of a well plate 100 having a well grid of 16 by 24 wells. FIG. 9 shows a portion of a well plate 101 having a well grid of 8 by 12 wells. FIG. 10 shows a pin 18 mounted on lid 10 having a coating 20 . | A thermal cycling device consisting of a plate containing a plurality of wells to hold liquid and a lid that covers the plate and contains a number of “pins” that insert into the wells of the plate to control the temperature of the sample in the well. Biological, chemical or other samples are placed into the wells of the plate and the lid is placed on the plate with the pins inserted into or in the proximity of the sample. The lid, the outer surface of which may be copper clad and in direct contract with the pins, is heated or cooled, rapidly and uniformly heating or cooling the biological samples. The temperature of the sample can be rapidly and uniformly cycled and is particularly useful for the amplification of DNA via the polymerase chain reaction. | 8 |
[0001] This application is a Divisional of U.S. patent application Ser. No. 09/978,725 filed Oct. 17, 2001, now pending and expressly incorporated by reference herein in its entirety.
FIELD OF THE INVENTION
[0002] This invention relates to novel dye-bioconjugates for use in diagnosis and therapy, particularly novel compositions of cyanine dye bioconjugates of bioactive molecules.
BACKGROUND OF THE INVENTION
[0003] Cancer will continue to be a primary cause of death for the foreseeable future, but early detection of tumors would improve patient prognosis (R. T. Greenlee et al., Cancer statistics, 2000, CA Cancer J. Clin., 2000, 50, pp. 7-33). Despite significant advances in current methods for the diagnosis of cancer, physicians still rely on the presence of a palpable tumor mass. At this, however, the many benefits of early medical intervention may have been already compromised.
[0004] Photodiagnosis and/or phototherapy has a great potential to improve management of cancer patient (D. A. Benaron and D. K. Stevenson, Optical time - of - flight and absorbance imaging of biologic media, Science, 1993, 259, pp. 1463-1466; R. F. Potter (Series Editor), Medical optical tomography. functional imaging and monitoring, SPIE Optical Engineering Press, Bellingham, 1993; G. J. Tearney et al., In vivo endoscopic optical biopsy with optical coherence tomography, Science, 1997, 276, pp. 2037-2039; B. J. Tromberg et al., Non - invasive measurements of breast tissue optical properties using frequency - domain photon migration, Phil. Trans. Royal Society London B, 1997, 352, pp. 661-668; S. Fantini et al., Assessment of the size, position, and optical properties of breast tumors in vivo by non - invasive optical methods, Appl. Opt., 1998, 37, pp.1982-1989; A. Pelegrin et al., Photoimmunodiagnosis with antibody - fluorescein conjugates: in vitro and in vivo preclinical studies, J. Cell Pharmacol., 1992, 3, pp. 141-145). These procedures use visible or near infrared light to induce the desired effect. Both optical detection and phototherapy have been demonstrated to be safe and effective in clinical settings and biomedical research (B. C. Wilson, Optical properties of tissues, Encyclopedia of Human Biology, 1991, 5, 587-597; Y-L. He et al., Measurement of blood volume using indocyanine green measured with pulse - spectrometry: Its reproducibility and reliability, Critical Care Medicine, 1998, 26, pp.1446-1451; J. Caesar et al., The use of Indocyanine green in the measurement of hepatic blood flow and as a test of hepatic function, Clin. Sci., 1961, 21, pp. 43-57; R. B. Mujumdar et al., Cyanine dye labeling reagents: Sulfoindocyanine succinimidyl esters, Bioconjugate Chemistry, 1993, 4, pp.105-111; U.S. Pat. No. 5,453,505; Eric Hohenschuh, et al., Light imaging contrast agents, WO 98/48846; Jonathan Turner, et al., Optical diagnostic agents for the diagnosis of neurodegenerative diseases by means of near infra - red radiation, WO 98/22146; Kai Licha, et al., In - vivo diagnostic process by near infrared radiation, WO 96/17628; Robert A. Snow, et al., Compounds, WO 98/48838].
[0005] Dyes are important to enhance signal detection and/or photosensitizing of tissues in optical imaging and phototherapy. Previous studies have shown that certain dyes can localize in tumors and serve as a powerful probe for the detection and treatment of small cancers (D. A. Bellnier et al., Murine pharmacokinetics and antitumor efficacy of the photodynamic sensitizer 2-[1- hexyloxyethyl ]-2- devinyl pyropheophorbide - a, J. Photochem. Photobiol., 1993, 20, pp. 55-61; G. A. Wagnieres et al., In vivo fluorescence spectroscopy and imaging for oncological applications, Photochem. Photobiol., 1998, 68, pp. 603-632; J. S. Reynolds et al., Imaging of spontaneous canine mammary tumors using fluorescent contrast agents, Photochem. Photobiol., 1999, 70, pp. 87-94). However, these dyes do not localize preferentially in malignant tissues.
[0006] Efforts have been made to improve the specificity of dyes to malignant tissues by conjugating dyes to large biomolecules (A. Pelegrin, et al., Photoimmunodiagnosis with antibody - fluorescein conjugates: in vitro and in vivo preclinical studies, J. Cell Pharmacol., 1992, 3, pp. 141-145; B. Ballou et al., Tumor labeling in vivo using cyanine - conjugated monoclonal antibodies, Cancer Immunol. Immunother., 1995, 41, pp. 257-263; R. Weissleder et al., In vivo imaging of tumors with protease - activated near - infrared fluorescent probes, Nature Biotech., 1999, 17, pp. 375-378; K. Licha et al., New contrast agents for optical imaging: Acid - cleavable conjugates of cyanine dyes with biomolecules, Proc. SPIE, 1999, 3600, pp. 29-35). Developing a dye that can combine the roles of tumor-seeking, diagnostic, and therapeutic functions has been very difficult for several reasons. The dyes currently in use localize in tumors by a non-specific mechanism that usually relies on the lipophilicity of the dye to penetrate the lipid membrane of the cell. These lipophilic dyes require several hours or days to clear from normal tissues, and low tumor-to-normal tissue ratios are usually encountered. Furthermore, combining photodynamic properties with fluorescence emission needed for the imaging of deep tissues requires a molecule that must compromise either the photosensitive effect of the dye or the fluorescence quantum yield. Photosensitivity of phototherapy agents relies on the transfer of energy from the excited state of the agent to surrounding molecules or tissues, while fluorescence emission demands that the excitation energy be emitted in the form of light (T. J. Dougherty et al., Photoradiation therapy II: Cure of animal tumors with hematoporphyrin and light, Journal of National Cancer Institute, 1978, 55, pp.115-121). Therefore, compounds and compositions that have optimal tumor-targeting ability to provide a highly efficient photosensitive agent for treatment of tumors are needed. Such agents would exhibit enhanced specificity for tumors and would also have excellent photophysical properties for optical detection.
[0007] Each of the references previously disclosed is expressly incorporated by reference herein in its entirety.
SUMMARY OF THE INVENTION
[0008] The invention is directed to a composition for a carbocyanine dye bioconjugate. The bioconjugate consists of three components: 1) a tumor specific agent, 2) a photosensitizer (phototherapy) agent, and 3) a photodiagnostic agent. The inventive bioconjugates use the multiple attachment points of carbocyanine dye structures to incorporate one or more receptor targeting and/or photosensitive groups in the same molecule. The composition may be used in various biomedical applications.
[0009] The invention is also directed to a method for performing a diagnostic and therapeutic procedure by administering an effective amount of the composition of the cyanine dye bioconjugate to an individual. The method may be used in various biomedical applications, such as imaging tumors, targeting tumors with anti-cancer drugs, and performing laser guided surgery.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] [0010]FIG. 1. shows representative structures of the inventive compounds.
[0011] [0011]FIG. 2 shows images taken at two minutes and 30 minutes post injection of indocyanine green into rats with various tumors.
[0012] [0012]FIG. 3 shows fluorescent images of a CA20948 tumor bearing rat taken at one and 45 minutes post administration of cytate.
[0013] [0013]FIG. 4 is a fluorescent image of a CA20948 tumor bearing rat taken at 27 hours post administration of cytate.
[0014] [0014]FIG. 5 shows fluorescent images of ex-vivo tissues and organs from a CA20948 tumor bearing rat at 27 hours post administration of cytate.
[0015] [0015]FIG. 6 is a fluorescent image of an AR42-J tumor bearing rat taken at 22 hours post administration of bombesinate.
DETAILED DESCRIPTION OF THE INVENTION
[0016] The invention relates to novel compositions comprising cyanine dyes having a general formula 1
[0017] wherein W 1 and W 2 may be the same or different and are selected from the group consisting of —CR 10 R 11 , —O—, —NR 12 , —S—, and —Se; Y 1 , Y 2 , Z 1 , and Z 2 are independently selected from the group consisting of hydrogen, tumor-specific agents, phototherapy agents, —CONH-Bm, —NHCO-Bm, —(CH 2 ) a —CONH-Bm, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —CONH-Bm, —(CH 2 )a—NHCO-Bm, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —NHCO-Bm, —(CH 2 ) a —N(R 12 )—(CH 2 ) b —CONH-Bm, —(CH 2 ) a —N(R 12 )—(CH 2 ) c —NHCO-Bm, —(CH 2 ) a —N(R 12 )—CH 2 —(CH 2 OCH 2 ) b —CH 2 —CONH-Bm, —(CH 2 ) a —N(R 12 )—CH 2 —(CH 2 OCH 2 ) b —CH 2 —NHCO-Bm, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —N(R 12 )—(CH 2 ) a —CONH-Bm, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —N(R 12 )—(CH 2 ) a —NHCO-Bm, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —N(R 12 ) —CH 2 —(CH 2 OCH 2 ) d —CONH-Bm, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —N(R 12 )—CH 2 —(CH 2 OCH 2 ) d —NHCO-Bm, —CONH-Dm, —NHCO-Dm, —(CH 2 ) a —CONH-Dm, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —CONH-Dm, —(CH 2 ) a —NHCO-Dm, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —NHCO-Dm, —(CH 2 ) a —N(R 12 )—(CH 2 ) b —CONH-Dm, —(CH 2 ) a —N(R 12 )—(CH 2 ) c —NHCO-Dm, —(CH 2 ) a —N(R 12 )—CH 2 —(CH 2 OCH 2 ) b —CH 2 —CONH-Dm, —(CH 2 ) a —N(R 12 )—CH 2 —(CH 2 OCH 2 ) b —CH 2 —NHCO-Dm, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —N(R 12 )—(CH 2 ) a —CONH-Dm, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —N(R 12 )—(CH 2 ) a —NHCO-Dm, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —N(R 12 )—CH 2 —(CH 2 OCH 2 ) d —CONH-Dm, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —N(R 12 )—CH 2 —(CH 2 OCH 2 ) d —NHCO-Dm, —(CH 2 ) a —N R 12 R 13 , and —CH 2 (CH 2 OCH 2 ) b —CH 2 N R 12 R 13 ; K 1 and K 2 are independently selected from the group consisting of C 1 -C 30 alkyl, C 5 -C 30 aryl, C 1 -C 30 alkoxyl, C 1 -C 30 polyalkoxyalkyl, C 1 -C 30 polyhydroxyalkyl, C 5 -C 30 polyhydroxyaryl, C 1 -C 30 aminoalkyl, saccharides, peptides, —CH 2 (CH 2 OCH 2 ) b —CH 2 —, —(CH 2 ) a —CO—, —(CH 2 ) a —CONH—, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —CONH—, —(CH 2 ) a —NHCO—, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —NHCO—, —(CH 2 ) a —O—, and —CH 2 —(CH 2 OCH 2 ) b —CO—; X 1 and X 2 are single bonds, or are independently selected from the group consisting of nitrogen, saccharides, —CR 14 —, —CR 14 R 15 , —NR 16 R 17 ; C 5 -C 30 aryl; Q is a single bond or is selected from the group consisting of —O—, —S—, —Se—, and —NR 18 ; a 1 and b 1 independently vary from 0 to 5; R 1 to R 13 , and R 18 are independently selected from the group consisting of hydrogen, C 1 -C 10 alkyl, C 5 -C 20 aryl, C 1 -C 10 alkoxyl, C 1 -C 10 polyalkoxyalkyl, C 1 -C 20 polyhydroxyalkyl, C 5 -C 20 polyhydroxyaryl, C 1 -C 10 aminoalkyl, cyano, nitro, halogens, saccharides, peptides, —CH 2 (CH 2 OCH 2 ) b —CH 2 —OH, —(CH 2 ) a —CO 2 H, —(CH 2 ) a —CONH-Bm, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —CONH-Bm, —(CH 2 ) a —NHCO-Bm, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —NHCO-Bm, —(CH 2 ) a —OH and —CH 2 —(CH 2 OCH 2 ) b —CO 2 H; R 14 to R 17 are independently selected from the group consisting of hydrogen, C 1 -C 10 alkyl, C 5 -C 20 aryl, C 1 -C 10 alkoxyl, C 1 -C 10 polyalkoxyalkyl, C 1 -C 20 polyhydroxyalkyl, C 5 -C 20 polyhydroxyaryl, C 1 -C 10 aminoalkyl, saccharides, peptides, —CH 2 (CH 2 OCH 2 ) b —CH 2 —, —(CH 2 ) a —CO—, —(CH 2 ) a —CONH—, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —CONH—, —(CH 2 ) a —NHCO—, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —NHCO—, —(CH 2 ) a —O—, and —CH 2 —(CH 2 OCH 2 ) b —CO—; Bm and Dm are independently selected from the group consisting of bioactive peptides, proteins, cells, antibodies, antibody fragments, saccharides, glycopeptides, peptidomimetics, drugs, drug mimics, hormones, metal chelating agents, radioactive or nonradioactive metal complexes, echogenic agents, photoactive molecules, and phototherapy agents (photosensitizers); a and c independently vary from 1 to 20; b and d independently vary from 1 to 100.
[0018] The invention also relates to the novel composition comprising carbocyanine dyes having a general formula 2
[0019] wherein W 1 , W 2 , Y 1 , Y 2 , Z 1 , Z 2 , K 1 , K 2 , Q, X 1 , X 2 , a 1 , and b 1 are defined in the same manner as in Formula 1; and R 19 to R 31 are defined in the same manner as R 1 to R 9 in Formula 1.
[0020] The invention also relates to the novel composition comprising carbocyanine dyes having a general formula 3
[0021] wherein A 1 is a single or a double bond; B 1 , C 1 , and D 1 are independently selected from the group consisting of —O—, —S—, —Se—, —P—, —CR 10 R 11 , —CR 11 , alkyl, NR 12 , and —C═O; A 1 , B 1 , C 1 , and D 1 may together form a 6- to 12-membered carbocyclic ring or a 6- to 12-membered heterocyclic ring optionally containing one or more oxygen, nitrogen, or sulfur atoms; and W 1 , W 2 , Y 1 , Y 2 , Z 1 , Z 2 , K 1 , K 2 , X 1 , X 2 , a 1 , b 1 , and R 1 to R 12 are defined in the same manner as in Formula 1.
[0022] The present invention also relates to the novel composition comprising carbocyanine dyes having a general formula 4
[0023] wherein A 1 , B 1 , C 1 , and D 1 are defined in the same manner as in Formula 3; W 1 , W 2 , Y 1 , Y 2 , Z 1 , Z 2 , K 1 , K 2 , X 1 , X 2 , a 1 , and b 1 are defined in the same manner as in Formula 1; and R 19 to R 31 are defined in the same manner as R 1 to R 9 in Formula 1.
[0024] The inventive bioconjugates use the multiple attachment points of carbocyanine dye structures to incorporate one or more receptor targeting and/or photosensitive groups in the same molecule. More specifically, the inventive compositions consist of three components selected for their specific properties. One component, a tumor specific agent, is for targeting tumors. A second component, which may be a photosensitizer, is a phototherapy agent. A third component is a photodiagnostic agent.
[0025] Examples of the tumor targeting agents are bioactive peptides such as octreotate and bombesin (7-14) which target overexpressed receptors in neuroendocrine tumors. An example of a phototherapy agent is 2-[1-hexyloxyethyl]-2-devinylpyro-pheophorbide-a (HPPH, FIG. 1D, T=OH). Examples of photodiagnostic agents are carbocyanine dyes which have high infrared molar absorbtivities (FIG. 1A-C). The invention provides each of these components, with their associated benefits, in one molecule for an optimum effect.
[0026] Such small dye biomolecule conjugates have several advantages over either nonspecific dyes or the conjugation of probes or photosensitive molecules to large biomolecules. These conjugates have enhanced localization and rapid visualization of tumors which is beneficial for both diagnosis and therapy. The agents are rapidly cleared from blood and non-target tissues so there is less concern for accumulation and for toxicity. A variety of high purity compounds may be easily synthesized for combinatorial screening of new targets, e.g., to identify receptors or targeting agents, and for the ability to affect the pharmacokinetics of the conjugates by minor structural changes.
[0027] The inventive compositions are useful for various biomedical applications. Examples of these applications include, but are not limited to: detecting, imaging, and treating of tumors; tomographic imaging of organs; monitoring of organ functions; performing coronary angiography, fluorescence endoscopy, laser guided surgery; and performing photoacoustic and sonofluorescent methods.
[0028] Specific embodiments to accomplish some of the aforementioned biomedical applications are given below. The inventive dyes are prepared according the methods well known in the art.
[0029] In two embodiments, the inventive bioconjugates have the formulas 1 or 2 where W 1 and W 2 may be the same or different and are selected from the group consisting of —C(CH 3 ) 2 , —C((CH 2 ) a OH)CH 3 , —C((CH 2 ) a OH) 2 , —C((CH 2 ) a CO 2 H)CH 3 , —C((CH 2 ) a CO 2 H) 2 , —C((CH 2 ) a NH 2 )CH 3 , —C((CH 2 ) a NH 2 ) 2 , —C((CH 2 ) a NR 12 R 13 ) 2 , —NR 12 , and —S—; Y 1 and Y 2 are selected from the group consisting of hydrogen, tumor-specific agents, —CONH-Bm, —NHCO-Bm, —(CH 2 ) a —CONH-Bm, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —CONH-Bm, —(CH 2 ) a —NHCO-Bm, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —NHCO-Bm, —(CH 2 ) a —NR 12 R 13 , and —CH 2 (CH 2 OCH 2 ) b —CH 2 NR 12 R 13 ; Z 1 and Z 2 are independently selected from the group consisting of hydrogen, phototherapy agents, —CONH-Dm, —NHCO-Dm, —(CH 2 ) a —CONH-Dm, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —CONH-Dm, —(CH 2 ) a —NHCO-Dm, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —NHCO-Dm, —(CH 2 ) a —N R 12 R 13 , and —CH 2 (CH 2 OCH 2 ) b —CH 2 N R 12 R 3 ; K 1 and K 2 are independently selected from the group consisting of C 1 -C 10 alkyl, C 5 -C 20 aryl, C 1 -C 20 alkoxyl, C 1 -C 20 aminoalkyl, —(CH 2 ) a —CO—, —(CH 2 ) a —CONH, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —CONH—, —(CH 2 ) a —NHCO—, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —NHCO—, and —CH 2 —(CH 2 OCH 2 ) b —CO—; X, and X 2 are single bonds, or are independently selected from the group consisting of nitrogen, —CR 14 —, —CR 14 R 15 , and —NR 16 R 17 ; Q is a single bond or is selected from the group consisting of —O—, —S—, and —NR 18 ; a 1 and b 1 independently vary from 0 to 3; Bm is selected from the group consisting of bioactive peptides containing 2 to 30 amino acid units, proteins, antibody fragments, mono- and oligosaccharides; Dm is selected from the group consisting of photosensitizers, photoactive molecules, and phototherapy agents; a and c independently vary from 1 to 20; and b and d independently vary from 1 to 100.
[0030] In two other embodiments, the bioconjugates according to the present invention have the formulas 3 or 4 wherein W 1 and W 2 may be the same or different and are selected from the group consisting of —C(CH 3 ) 2 , —C((CH 2 ) a OH)CH 3 , —C((CH 2 ) a OH) 2 , —C((CH 2 ) a CO 2 H)CH 3 , —C((CH 2 ) a CO 2 H) 2 , —C((CH 2 ) a NH 2 )CH 3 , —C((CH 2 ) a NH 2 ) 2 , —C((CH 2 ) a NR 12 R 3 ) 2 , —NR 2 , and —S—; Y 1 and Y 2 are selected from the group consisting of hydrogen, tumor-specific agents, —CONH-Bm, —NHCO-Bm, —(CH 2 ) a —CONH-Bm, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —CONH-Bm, —(CH 2 ) a —NHCO-Bm, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —NHCO-Bm, —(CH 2 ) a —NR 12 R 13 , and —CH 2 (CH 2 OCH 2 ) b —CH 2 NR 12 R 13 ; Z 1 and Z 2 are independently selected from the group consisting of hydrogen, phototherapy agents, —CONH-Dm, —NHCO-Dm, —(CH 2 ) a —CONH-Dm, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —CONH-Dm, —(CH 2 ) a —NHCO-Dm, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —NHCO-Dm, —(CH 2 ) a —N R 12 R 13 , and —CH 2 (CH 2 OCH 2 ) b —CH 2 N R 12 R 13 ; K 1 and K 2 are independently selected from the group consisting of C 1 -C 10 alkyl, C 5 -C 20 aryl, C 1 -C 20 alkoxyl, C 1 -C 20 aminoalkyl, —(CH 2 ) a —CO—, —(CH 2 ) a —CONH, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —CONH—, —(CH 2 ) a —NHCO—, —CH 2 —(CH 2 OCH 2 ) b —CH 2 —NHCO—, and —CH 2 —(CH 2 OCH 2 ) b —CO—; X 1 and X 2 are single bonds or are independently selected from the group consisting of nitrogen, —CR 14 —, —CR 14 R 15 , and —NR 16 R 17 ; A 1 is a single or a double bond; B 1 , C 1 , and D 1 are independently selected from the group consisting of —O—, —S, —CR 11 , alkyl, NR 12 , and —C═O; A 1 , B 1 , C 1 , and D 1 may together form a 6- to 1 2-membered carbocyclic ring or a 6- to 12-membered heterocyclic ring optionally containing one or more oxygen, nitrogen, or sulfur atoms; a 1 and b 1 independently vary from 0 to 3; Bm is selected from the group consisting of bioactive peptides containing 2 to 30 amino acid units, proteins, antibody fragments, mono- and oligosaccharides; bioactive peptides, protein, and oligosaccharide; Dm is selected from the group consisting of photosensitizers, photoactive molecules, and phototherapy agents; a and c independently vary from 1 to 20; and b and d independently vary from 1 to 100.
[0031] In one embodiment of the invention, the dye-biomolecule conjugates are useful for optical tomographic, endoscopic, photoacoustic and sonofluorescent applications for the detection and treatment of tumors and other abnormalities. These methods use light of wavelengths in the region of 300-1300 nm. For example, optical coherence tomography (OCT), also referred to as “optical biopsy,” is an optical imaging technique that allows high resolution cross sectional imaging of tissue microstructure. OCT methods use wavelengths of about 1280 nm.
[0032] In various aspects of the invention, the dye-biomolecule conjugates are useful for localized therapy for the detection of the presence or absence of tumors and other pathologic tissues by monitoring the blood clearance profile of the conjugates, for laser assisted guided surgery (LAGS) for the detection and treatment of small micrometastases of tumors, e.g., somatostatin subtype 2 (SST-2) positive tumors, upon laparoscopy, and for diagnosis of atherosclerotic plaques and blood clots.
[0033] In another embodiment, a therapeutic procedure comprises attaching a porphyrin or photodynamic therapy agent to a bioconjugate, and then administering light of an appropriate wavelength for detecting and treating an abnormality.
[0034] The compositions of the invention can be formulated for enteral or parenteral administration. These formulations contain an effective amount of the dye-biomolecule conjugate along with conventional pharmaceutical carriers and excipients appropriate for the type of administration contemplated. For example, parenteral formulations advantageously contain a sterile aqueous solution or suspension of the inventive conjugate, and may be injected directly, or may be mixed with a large volume parenteral composition or excipient for systemic administration as is known to one skilled in the art. These formulations may also contain pharmaceutically acceptable buffers and/or electrolytes such as sodium chloride.
[0035] Formulations for enteral administration may vary widely, as is well known in the art. In general, such formulations are aqueous solutions, suspensions or emulsions which contain an effective amount of a dye-biomolecule conjugate. Such enteral compositions may include buffers, surfactants, thixotropic agents, and the like. Compositions for oral administration may also contain flavoring agents and other ingredients for enhancing their organoleptic qualities.
[0036] The inventive compositions of the carbocyanine dye bioconjugates for diagnostic uses are administered in doses effective to achieve the desired effect. Such doses may vary widely, depending upon the particular conjugate employed, the organs or tissues which are the subject of the imaging procedure, the imaging equipment being used, and the like. The compositions may be administered either systemically, or locally to the organ or tissue to be imaged, and the patient is then subjected to diagnostic imaging and/or therapeutic procedures.
[0037] The present invention is further detailed in the following Examples, which are offered by way of illustration and are not intended to limit the scope of the invention in any manner.
EXAMPLE 1
Synthesis of Indocyaninebispropanoic Acid Dye (FIG. 1 A, n=1)
[0038] A mixture of 1,1,2-trimethyl-[1H]-benz[e]indole (9.1 g, 43.58 mmoles) and 3-bromopropanoic acid (10.0 g, 65.37 mmoles) in 1,2-dichlorobenzene (40 ml) was heated at 110° C. for 12 hours. The solution was cooled to ambient temperature. The red residue obtained was filtered and washed with acetonitrile:diethyl ether (1:1 v/v ) mixture. The solid obtained was dried at ambient temperature under vacuum to give 10 g (64%) of light brown powder.
[0039] A portion of this solid (6.0 g; 16.56 mmoles), glutaconic aldehyde dianilide hydrochloride (Lancaster Synthesis, Windham, N.H.) (2.36 g, 8.28 mmoles), and sodium acetate trihydrate (2.93 g, 21.53 mmoles) in ethanol (150 ml) were refluxed for 90 minutes. After evaporating the solvent, 40 ml of a 2 N aqueous HCl was added to the residue. The mixture was centrifuged and the supernatant was decanted. This procedure was repeated until the supernatant became nearly colorless. About 5 ml of a water:acetonitrile (3:2 v/v ) mixture was added to the solid residue and lyophilized to obtain 2 g of dark green flakes. The purity of the compound was established with 1 H-nuclear magnetic resonance ( 1 H-NMR) and liquid chromatography/mass spectrometry (LC/MS) as is known to one skilled in the art.
EXAMPLE 2
Synthesis of Indocyaninebishexanoic Acid Dye (FIG. 1 A, n=4)
[0040] A mixture of 1,1,2-trimethyl-[1H]-benz[e]indole (20 g, 95.6 mmoles) and 6-bromohexanoic acid (28.1 g, 144.1 mmoles) in 1,2-dichlorobenzene (250 ml) was heated at 110 C for 12 hours. The green solution was cooled to ambient temperature and the brown solid precipitate that formed was collected by filtration. After washing the solid with 1,2-dichlorobenzene and diethyl ether, the brown powder obtained (24 g, 64%) was dried under vacuum at ambient temperature. A portion of this solid (4.0 g; 9.8 mmoles) glutacoaldehyde dianil monohydrochloride (1.4 g, 5 mmoles) and sodium acetate trihydrate (1.8 g, 12.9 mmoles) in ethanol (80 ml) were refluxed for 1 hour. After evaporating the solvent, 20 ml of 2 N aqueous HCl was added to the residue. The mixture was centrifuged and the supernatant was decanted. This procedure was repeated until the supernatant became nearly colorless. About 5 ml of a water:acetonitrile (3:2 v/v ) mixture was added to the solid residue and lyophilized to obtain about 2 g of dark green flakes. The purity of the compound was established with 1 H-NMR and LC/MS.
EXAMPLE 3
Synthesis of Peptides
[0041] Peptides of this invention were prepared by similar procedures with slight modifications in some cases.
[0042] Octreotate, an octapeptide, has the amino acid sequence D-Phe-Cys′-Tyr-D-Trp-Lys-Thr-Cys′-Thr (SEQ ID NO:1), wherein Cys′ indicates the presence of an intramolecular disulfide bond between two cysteine amino acids. Octreotate was prepared by an automated fluorenylmethoxycarbonyl (Fmoc) solid phase peptide synthesis using a commercial peptide synthesizer from Applied Biosystems (Model 432A SYNERGY Peptide Synthesizer). The first peptide cartridge contained Wang resin pre-loaded with Fmoc-Thr on a 25-μmole scale. Subsequent cartridges contained Fmoc-protected amino acids with side chain protecting groups for the following amino acids: Cys(Acm), Thr(t-Bu), Lys(Boc), Trp(Boc) and Tyr(t-Bu). The amino acid cartridges were placed on the peptide synthesizer and the product was synthesized from the C- to the N-terminal position according to standard procedures. The coupling reaction was carried out with 75 μmoles of the protected amino acids in the presence of 2-(1H-benzotriazol-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate (HBTU)/N-hydroxybenzotriazole (HOBt). The Fmoc protecting groups were removed with 20% piperidine in dimethylformamide.
[0043] After the synthesis was complete, the thiol group was cyclized with thallium trifluoroacetate and the product was cleaved from the solid support with a cleavage mixture containing trifluoroacetic acid water:phenol:thioanisole (85:5:5:5 v/v ) for 6 hours. The peptide was precipitated with t-butyl methyl ether and lyophilized with water:acetonitrile (2:3 v/v ). The peptide was purified by HPLC and analyzed by LC/MS.
[0044] Octreotide, (D-Phe-Cys′-Tyr-D-Trp-Lys-Thr-Cys′-Thr-OH (SEQ ID NO:2)), wherein Cys′ indicates the presence of an intramolecular disulfide bond between two cysteine amino acids) was prepared by the same procedure as that for octreotate with no modifications.
[0045] Bombesin analogs were prepared by the same procedure but cyclization with thallium trifluoroacetate was omitted. Side-chain deprotection and cleavage from the resin was carried out with 50 μl each of ethanedithiol, thioanisole and water, and 850 μl of trifluoroacetic acid. Two analogues were prepared:
Gly-Ser-Gly-Gln-Trp-Ala-Val-Gly-His- (SEQ ID NO: 3) Leu-Met-NH 2 and Gly-Asp-Gly-Gln-Trp-Ala-Val-Gly-His- (SEQ ID NO: 4) Leu-Met-NH 2 .
[0046] Cholecystokinin octapeptide analogs were prepared as described for Octreotate without the cyclization step. Three analogs were prepared: Asp-Tyr-Met-Gly-Trp-Met-Asp-Phe-NH 2 (SEQ ID NO:5); Asp-Tyr-Nle-Gly-Trp-Nle-Asp-Phe—NH 2 (SEQ ID NO:6); and D-Asp-Tyr-Nle-Gly-Trp-Nle-Asp-Phe-NH 2 (SEQ ID NO:7) wherein Nle is norleucine.
[0047] Neurotensin analog (D-Lys-Pro-Arg-Arg-Pro-Tyr-Ile-Leu (SEQ ID NO:8)) was prepared as described for Octreotate without the cyclization step.
EXAMPLE 4
Synthesis of Peptide-Dye Conjugates (FIG. 1 B, n=1, R 1 =Octreotate, R 2 ═R 1 or OH)
[0048] The method described below is for the synthesis of Octreotate-cyanine dye conjugates. Similar procedures were used for the synthesis of other peptide-dye conjugates.
[0049] Octreotate was prepared as described in Example 3, but the peptide was not cleaved from the solid support and the N-terminal Fmoc group of Phe was retained. The thiol group was cyclized with thallium trifluoroacetate and Phe was deprotected to liberate the free amine.
[0050] Bisethylcarboxymethylindocyanine dye (53 mg, 75 μmoles) was added to an activation reagent consisting of a mixture 0.2 M HBTU/HOBt in DMSO (375 μl), and 0.2 M diisopropylethylamine in DMSO (375 μl). The activation was complete in about 30 minutes. The resin-bound peptide (25 μmoles) was then added to the dye. The coupling reaction was carried out at ambient temperature for 3 hours. The mixture was filtered and the solid residue was washed with DMF, acetonitrile and THF. After drying the green residue, the peptide was cleaved from the resin, and the side chain protecting groups were removed with a mixture of trifluoroacetic acid: water:thioanisole:phenol (85:5:5:5 v/v ). The resin was filtered and cold t-butyl methyl ether (MTBE) was used to precipitate the dye-peptide conjugate. The conjugate was dissolved in acetonitrile:water (2:3 v/v ) and lyophilized.
[0051] The product was purified by HPLC to give the monooctreotate-bisethylcarboxymethylindocyanine dye (Cytate 1, 80%, n=1, R 2 ═OH) and the bisoctreotate-bisethylcarboxymethylindocyanine dye (Cytate 2, 20%, n=1, R 1 ═R 2 ).
[0052] The monooctreotate conjugate may be obtained almost exclusively (>95%) over the bis conjugate by reducing the reaction time to 2 hours. This, however, leads to an incomplete reaction, and the free octreotate must be carefully separated from the dye conjugate in order to avoid saturation of the receptors by the non-dye conjugated peptide.
EXAMPLE 5
Synthesis of Peptide-Dye Conjugates (FIG. 1 B, n=4 R 1 =octreotate, R 2 ═R 1 or OH)
[0053] Octreotate-bispentylcarboxymethylindocyanine dye was prepared as described in Example 4 with some modifications. Bispentylcarboxymethyl-indocyanine dye (60 mg, 75 μmoles) was added to 400 μl activation reagent consisting of 0.2 M HBTU/HOBt and 0.2 M diisopropylethylamine in DMSO. The activation was complete in about 30 minutes and the resin-bound peptide (25 μmoles) was added to the dye. The reaction was carried out at ambient temperature for 3 hours. The mixture was filtered and the solid residue was washed with DMF, acetonitrile and THF. After drying the green residue, the peptide was cleaved from the resin and the side chain protecting groups were removed with a mixture of trifluoroacetic acid:water:thioanisole:phenol (85:5:5:5 v/v ). The resin was filtered and cold t-butyl methyl ether (MTBE) was used to precipitate the dye-peptide conjugate. The conjugate was dissolved in acetonitrile:water (2:3 v/v ) and lyophilized. The product was purified by HPLC to give octreotate-1,1,2-trimethyl-[1H]-benz[e]indole propanoic acid conjugate (10%), monooctreotate-bispentylcarboxymethylindocyanine dye (Cytate 3, 60%, n=4, R 2 ═OH) and bisoctreotate-bispentylcarboxymethylindocyanine dye (Cytate 4, 30%, n=4, R 1 ═R 2 ).
EXAMPLE 6
Synthesis of Peptide-Dye-Phototherapy Conjugates (FIG. 1 B, n=4, R 1 =Octreotate, R 2 =HPPH) by Solid Phase
[0054] Bispentylcarboxymethylindocyanine dye (cyhex, 60 mg, 75 μmoles) in dichloromethane is reacted with cyanuric acid fluoride (21 mg, 150 mmoles) in the presence of pyridine (12 mg, 150 mmoles) for 30 minutes to produce an acid anhydride. One molar equivalent of 2-[1 -hexyloxyethyl]-2-devinylpyropheophorbide-a (HPPH, FIG. 1D, T=—NHC 2 H 4 NH 2 ) is added to the anhydride to form the cyhex-HPPH conjugate with a free carboxylic acid group. This intermediate is added to an activation reagent consisting of a 0.2 M solution of HBTU/HOBt in DMSO (400 μl), and a 0.2 M solution of diisopropylethylamine in DMSO (400 μl). Activation of the carboxylic acid is complete in about 30 minutes. Resin-bound peptide (octreotate, 25 μmoles), prepared as described in Example 4, is added to the mixture. The reaction is carried out at ambient temperature for 8 hours. The mixture is filtered and the solid residue is washed with DMF, acetonitrile and THF. After drying the dark residue at ambient temperature, the peptide derivative is cleaved from the resin and the side chain protecting groups are removed with a mixture of trifluoroacetic acid:water:thioanisole:phenol (85:5:5:5 v/v ). After filtering the resin, cold t-butyl methyl ether (MTBE) is used to precipitate the dye-peptide conjugate, which is then lyophilized in acetonitrile:water (2:3 v/v ).
EXAMPLE 7
Synthesis of Peptide-Dye-Phototherapy Conjugates (FIG. 1 B, n=4, R 1 =Octreotide. R 2 =HPPH) by Solution Phase
[0055] Derivatized HPPH ethylenediamine (FIG. 1D, T=—NHC 2 H 4 NH 2 ; 1.1 molar equivalents) and lysine(trityl) 4 octreotide (1.2 molar equivalents) were added to a solution of bis(pentafluorophenyl) ester of cyhex (1 molar equivalent) in DMF. After stirring the mixture for 8 hours at ambient temperature, cold t-butyl methyl ether was added to precipitate the peptide conjugate. The crude product was purified by high performance liquid chromatography (HPLC).
EXAMPLE 8
Synthesis of Peptide-Dye-Phototherapy Conjugates (FIG. 1 C, n=4, R 1 =K 0 -Octreotate, R 2 =HPPH, R 3 =OH) by Solid Phase
[0056] Orthogonally protected Fmoc-lysine(Mtt) 0 Octreotate was prepared on a solid support, as described in Examples 3 and 4. The Fmoc group of Fmoc-lysine(Mtt) 0 is removed from the solid support with 20% piperidine in DMF. HPPH (FIG. 1D, T=—OH), pre-activated with HBTU coupled to the free α-amino group of lysine.
EXAMPLE 9
Imaging of Tumor Cell Lines With Indocyanine Green
[0057] A non-invasive in vivo fluorescence imaging apparatus was employed to assess the efficacy of indocyanine green (ICG) in three different rat tumor cell lines of the inventive contrast agents developed for tumor detection in animal models. A LaserMax Inc. laser diode of nominal wavelength 780 nm and nominal power of 40 mW was used. The detector was a Princeton Instruments model RTE/CCD-1317-K/2 CCD camera with a Rodenstock 10 mm F2 lens (stock #542.032.002.20) attached. An 830 nm interference lens (CVI Laser Corp., part #F10-8304-2) was mounted in front of the CCD input lens, such that only emitted fluorescent light from the contrast agent was imaged.
[0058] Three tumor cell lines, DSL 6/A (pancreatic), Dunning R3327-H (prostate), and CA20948 (pancreatic), which are rich in somatostatin (SST-2) receptors were induced into male Lewis rats by solid implant technique in the left flank area (Achilefu et al., Invest. Radiology, 2000, pp. 479-485). Palpable masses were detected nine days post implant.
[0059] The animals were anesthetized with xylazine:ketamine:acepromazine (1.5:1.5:0.5 v/v ) at 0.8 ml/kg via intramuscular injection. The left flank was shaved to expose the tumor and surrounding surface area. A 21-gauge butterfly needle equipped with a stopcock connected to two syringes containing heparinized saline was placed into the tail vein of the rat. Patency of the vein was checked prior to administration of ICG. Each animal was administered a 0.5 ml dose of a 0.42 mg/ml solution of ICG in saline.
[0060] Two of the cell lines, DSL 6/A (pancreatic) and Dunning R3327-H (prostate) which are rich in somatostatin (SST-2) receptors indicated slow perfusion of the agent into the tumor over time. Images were taken at 2 minutes and 30 minutes post administration of ICG. Reasonable images were obtained for each. The third line, CA20948 (pancreatic), indicated only a slight and transient perfusion that was cleared after only 30 minutes post injection. This indicated that there was no non-specific localization of ICG into this tumor line compared to the other two lines which suggested a vastly different vascular architecture for this type of tumor (FIG. 2). The first two tumor lines (DSL 6/A and R3327-H) were not as highly vascularized as CA20948 which is also rich in somatostatin (SST-2) receptors. Consequently, the detection and retention of a dye in the CA20948 tumor model is an important index of receptor-mediated specificity.
EXAMPLE 10
Imaging of Rat Pancreatic Acinar Carcinoma (CA20948) With Cytate 1
[0061] The peptide, octreotate, is known to target somatostatin (SST-2) receptors. Therefore, the cyano-octreotates conjugate, Cytate 1, was prepared as described in Example 4. The pancreatic acinar carcinoma, CA20948, was induced into male Lewis rats as described in Example 9.
[0062] The animals were anesthetized with xylazine:ketamine:acepromazine (1.5:1.5:0.5 v/v ) at 0.8 ml/kg via intramuscular injection. The left flank was shaved to expose the tumor and surrounding surface area. A 21-gauge butterfly needle equipped with a stopcock connected to two syringes containing heparinized saline was placed into the tail vein of the rat. Patency of the vein was checked prior to administration of Cytate 1 via the butterfly apparatus. Each animal was administered a 0.5 ml dose of a 1.0 mg/ml solution of Cytate 1 in 25% (v/v) dimethylsulfoxide/water.
[0063] Using the CCD camera apparatus, dye localization in the tumor was observed. Usually, an image of the animal was taken pre-injection of contrast agent, and the pre-injection image was subsequently subtracted (pixel by pixel) from the post-injection images to remove background. However, the background subtraction was not done if the animal had been removed from the sample area and was later returned for imaging several hours post injection. These images demonstrated the specificity of cytate 1 for the SST-2 receptors present in the CA20948 rat tumor model.
[0064] At one minute post administration of cytate 1 the fluorescent image suggested the presence of the tumor in the left flank of the animal (FIG. 3 a ). At 45 minutes post administration, the image showed green and yellow areas in the left and right flanks and in the tail, however, there was a dark blue/blue green area in the left flank (FIG. 3 b ). AT 27 hours post administration of the conjugate, only the left flank showed a blue/blue green fluorescent area (FIG. 4).
[0065] Individual organs were removed from the CA20948 rat which was injected with cytate 1 and were imaged. High uptake of the conjugate was observed in the pancreas, adrenal glands and tumor tissue. Significant lower uptake was observed in heart, muscle, spleen and liver (FIG. 5). These results correlated with results obtained using radiolabeled octreotate in the same rat model system (M. de Jong, et al. Cancer Res. 1998, 58, 437-441).
EXAMPLE 11
Imaging of Rat Pancreatic Acinar Carcinoma (AR42-J) with Bombesinate
[0066] The AR42-J cell line is derived from exocrine rat pancreatic acinar carcinoma. It can be grown in continuous culture or maintained in vivo in athymic nude mice, SCID mice, or in Lewis rats. This cell line is particularly attractive for in vitro receptor assays, as it is known to express a variety of hormone receptors including cholecystokinin (CCK), epidermal growth factor (EGF), pituitary adenylate cyclase activating peptide (PACAP), somatostatin (sst 2 ) and bombesin.
[0067] In this model, male Lewis rats were implanted with solid tumor material of the AR42-J cell line in a manner similar to that described in Example 9. Palpable masses were present 7 days post implant, and imaging studies were conducted on animals when the mass had achieved approximately 2 to 2.5 g (10-12 days post implant).
[0068] [0068]FIG. 6 shows the image obtained with this tumor model at 22 hours post injection of bombesinate. Uptake of bombesinate was similar to that described in Example 10 for uptake of cytate 1 with specific localization of the bioconjugate in the tumor.
EXAMPLE 12
Imaging of Rat Pancreatic Acinar Carcinoma (CA20948) with Cytate 1 by Fluorescence Endoscopy
[0069] Fluorescence endoscopy is suitable for tumors or other pathologic conditions of any cavity of the body. It is very sensitive and is used to detect small cancerous tissues, especially in the lungs and gastrointestinal (GI) system. Methods and procedures for fluorescence endoscopy are well-documented [Tajiri H., et al. Fluorescent diagnosis of experimental gastric cancer using a tumor-localizing photosensitizer. Cancer Letters (1997) 111, 215-220; Sackmann M., Fluorescence diagnosis in GI endoscop, Endoscopy (2000) 32, 977-985, and references therein].
[0070] The fluorescence endoscope consists of a small optical fiber probe inserted through the working channel of a conventional endoscope. Some fibers within this probe deliver the excitation light at 780 nm and others detect the fluorescence from the injected optical probe at 830 nm. The fluorescence intensity is displayed on a monitor.
[0071] Briefly, the CA20948 rat pancreatic tumor cells which are over-expressing somatostatin receptor are injected into the submucosa of a Lewis rat. The tumor is allowed to grow for two weeks. The rat is then anesthetized with xylazine:ketamine:acepromazine (1.5:1.5:0.5/ v/v ) at 0.8 mL/kg via intramuscular injection. Cytate is injected in the tail vein of the rat and 60 minutes post-injection, the endoscope is inserted into the GI tract. Since cytate localizes in CA20948, the fluorescence intensity in the tumor is much higher than in the surrounding normal tissues. Thus, the relative position of the tumor is determined by observing the image on a computer screen.
EXAMPLE 13
Imaging of Rat Pancreatic Acinar Carcinoma (CA20948) with Cytate 1 by Photoacoustic Technique
[0072] The photoacoustic imaging technique combines optical and acoustic imaging to allow better diagnosis of pathologic tissues. The preferred acoustic imaging method is ultrasonography where images are obtained by irradiating the animal with sound waves. The dual ultrasonography and optical tomography enables the imaging and localization of pathologic conditions (e.g., tumors) in deep tissues. To enhance the imaging, cytate is incorporated into ultrasound contrast material. Methods for the encapsulation of gases in biocompatible shells that are used as the contrast material are described in the literature [Mizushige K., et al., Enhancement of ultrasound - accelerated thrombolysis by echo contrast agents: dependence on microbubble structure, Ultrasound in Med. & Biol. (1999), 25,1431-1437]. Briefly, perfluorocarbon gas (e.g., perfluorobutane) is bubbled into a mixture of normal saline:propylene glycol:glycerol (7:1.5:1.5v/v/v) containing 7 mg/ml of cytate:dipalmitoylphosphatidylcholine:dipalmitoylphosphatidic acid, and dipalmitoylphosphatidylethanolamine-PEG 5,000 (1:7:1:1 mole %). The CA20948 tumor bearing Lewis rat is injected with 1 ml of the microbubbles and the agent is allowed to accumulate in the tumor. An optical image is obtained by exciting the near infrared dye at 780 nm and detecting the emitted light at 830 nm, as described in Examples 9-11. Ultrasonography is performed by irradiating the rat with sound waves in the localized tumor region and detecting the reflected sound as described in the literature [Peter J. A. Frinking, Ayache Bouakaz, Johan Kirkhorn, Folkert J. Ten Cate and Nico de Jong, Ultrasound contrast imaging: current and new potential methods, Ultrasound in Medicine & Biology (2000) 26, 965-975].
EXAMPLE 14
Photodynamic Therapy (PDT) and Localized Therapy of Rat Pancreatic Acinar Carcinoma (CA20948) with Cytate-PDT Agent Bioconjugates
[0073] The method for photodynamic therapy is well documented in the literature [Rezzoug H., et al. In Vivo Photodynamic Therapy with meso - Tetra ( m - hydroxyphenyl ) chlorin ( mTHPC ): Influence of Light Intensity and Optimization of Photodynamic Efficiency, Proc. SPIE (1996), 2924, 181-186; Stranadko E., et al. Photodynamic Therapy of Recurrent Cancer of Oral Cavity, an Alternative to Conventional Treatment, Proc. SPIE (1996), 2924, 292-297]. A solution of the peptide-dye-phototherapy bioconjugate is prepared as described in Example 7 (5 μmol/mL of 15% DMSO in water, 0.5 mL) and is injected into the tail vein of the tumor-bearing rat. The rat is imaged 24 hours post injection as described in Examples 9-11 to localize the tumor. Once the tumor region is localized, the tumor is irradiated with light of 700 nm (which corresponds to the maximum absorption wavelength of HPPH, the component of the conjugate that effects PDT). The energy of radiation is 10 J/cm 2 at 160 mW/cm 2 . The laser light is transmitted through a fiber optic, which is directed to the tumor. The rat is observed for 7 days and any decrease in tumor volume is noted. If the tumor is still present, a second dose of irradiation is repeated as described above until the tumor is no longer palpable.
[0074] For localized therapy, a diagnostic amount of cytate (0.5 mL/0.2 kg rat) is injected into the tail vein of the tumor-bearing rat and optical images are obtained as described in Examples 9-11. A solution of the peptide-dye-phototherapy bioconjugate is prepared as described in Example 7 (5 μmol/mL of 15% DMSO in water, 1.5 mL) and is injected directly into the tumor. The tumor is irradiated as described above.
EXAMPLE 15
Photodiagnosis with Atherosclerotic Plaques and Blood Clots
[0075] A solution of a peptide-dye-bioconjugate for targeting atherosclerotic plaques and associated blood clots is prepared as described in Example 7. The procedure for injecting the bioconjugate and subsequent localization and diagnosis of the plaques and clots is performed as described in Example 14.
[0076] While the invention has been disclosed by reference to the details of preferred embodiments of the invention, it is to be understood that the disclosure is intended in an illustrative rather than in a limiting sense, as it is contemplated that modifications will readily occur to those skilled in the art, within the spirit of the invention and the scope of the appended claims.
1
8
1
8
PRT
Artificial Sequence
MOD RES
(1)...(8)
Xaa at location 1 represents D-Phe. Artificial
sequence is completely synthesized.
1
Xaa Xaa Tyr Xaa Lys Thr Xaa Thr
1 5
2
8
PRT
Artificial Sequence
MOD RES
(1)...(8)
Xaa at location 1 represents D-Phe. Artificial
sequence is completely synthesized.
2
Xaa Xaa Tyr Xaa Lys Thr Xaa Xaa
1 5
3
11
PRT
Unknown
MOD RES
(1)...(11)
Bombesin analog
3
Gly Ser Gly Gln Trp Ala Val Gly His Leu Met
1 5 10
4
11
PRT
Unknown
MOD RES
(1)...(11)
Bombesin analog
4
Gly Asp Gly Gln Trp Ala Val Gly His Leu Met
1 5 10
5
8
PRT
Unknown
MOD RES
(1)...(8)
Cholecystokinin octapeptide analogs
5
Asp Tyr Met Gly Trp Met Asp Phe
1 5
6
8
PRT
Artificial Sequence
MOD RES
(1)...(8)
Xaa at locations 3 and 6 represents Norleucine.
Artificial sequence is completely synthesized.
6
Asp Tyr Xaa Gly Trp Xaa Asp Phe
1 5
7
8
PRT
Artificial Sequence
MOD RES
(1)...(8)
Xaa at location 1 represents D-Asp. Artificial
sequence is completely synthesized.
7
Xaa Tyr Xaa Gly Trp Xaa Asp Phe
1 5
8
8
PRT
Artificial Sequence
MOD RES
(1)...(8)
Xaa at location 1 represents D-Lys. Artificial
sequence is completely synthesized.
8
Xaa Pro Arg Arg Pro Tyr Ile Leu
1 5 | Novel tumor specific phototherapeutic and photodiagnostic agents are disclosed. The compounds consist of a carbocyanine dye for visualization, photosensitizer for photodynamic treatment, and tumor receptor-avid peptide for site-specific delivery of the probe and phototoxic agent to diseased tissues. A combination of these elements takes full advantage of the unique and efficient properties of each component for an effective patient care management. | 2 |
FIELD OF THE INVENTION
The present invention relates to the field of devices that can be used to load catalyst present in the form of solid particles into multitubular reactors.
The particular nature of the loading medium concerned in the present invention is that it is constituted by the annular zone comprised between an outer tube and an inner tube.
This type of tube is usually termed a “bayonet” tube. The catalyst itself is constituted by particles that are generally cylindrical in shape, with a diameter of approximately 1 to 2 cm, and a length in the range 0.5 cm to 2 cm.
The present invention is not linked to a particular chemical reaction, but more generally concerns any reactor that uses bayonet tube type tube technology.
As an example, the reactors with which the present invention are concerned are large capacity natural gas steam reforming reactors for the production of synthesis gas (typically 100000 Nm 3 /h). Such reactors are typically constituted by an assembly of approximately 200 to 300 tubes 15 meters in height enclosed in a shell that may reach 15 meters in diameter.
A major problem encountered in loading such multitubular reactors is that of homogeneity of the density of loading between the various catalytic tubes.
Any heterogeneity in loading will result in a difference in the density of loading that may produce preferential passages from one tube to another, or even within the same tube. It is essential that the loading method employed ensures good homogeneity of density between the various catalytic tubes.
The loading method associated with the device must also be reproducible and sufficiently rapid so that the loading time remains within reasonable limits.
EXAMINATION OF THE PRIOR ART
The prior art in the field of loading catalytic reactors is represented by two major types of loading, termed “dense” loading and “sock” loading. The first of these loading techniques consists in distributing the particles of catalyst inside the reactor by causing said particles to rotate and to allow them to fall in the manner of raindrops.
That method results in dense, homogeneous loading but requires equipment for causing rotation that can distribute the catalyst over several radii in order to cover all of the catalytic section properly.
The other method, termed “sock” loading, consists in introducing the particles of catalyst into the reactor through a flexible sock that is gradually lifted upwards as the level of particles of catalyst that are dispensed rises in the reactor. That method results in less dense loading than in “dense” loading, but the equipment is simpler.
The references below describe in more detail certain other loading methods used for industrial reactors:
UNIDENSE catalyst loading for steam reformers, published in 2008 in a commercial brochure from Johnson Matthey; Damand M B, Erikstrup N H B, Marcher J, Nielsen H C L T and Kelling D: Loading of steam reforming reactors using the “Spiraload Method”, in Ammonia Technical Manual 2003, an article by Haldor Topsoe; “Spiraload Technology” 2008, in the commercial brochure by Haldor Topsoe.
The prior art methods do not deal with the problem of loading catalyst inside tubes having an annular zone defined between an outer tube and an inner tube, termed bayonet tubes by the skilled person, in a satisfactory manner.
The space available in the annular zone of a bayonet tube is typically of the order of 50 mm, i.e. about half that of a simple tube with a diameter of 100 mm. Further, the need to maintain the constancy of the annular space, i.e. good concentricity between the inner tube and the outer tube, means that elements termed centralizers have to be installed between the outer tube and the inner tube, which centralizers are constituted, for example, by tabs fixed to one of the tubes, or tie rods connecting the walls of the inner and outer tubes.
Generally, said centralizers are 2 to 6 in number, and preferably 3 in number, over a given section. For a 15 m long bayonet tube, it may be necessary to distribute these centralizers over 4 or 5 levels distributed in a regular manner along the tube.
In the remainder of the text, the term “angular sector” will be used to designate the portion of space included between two consecutive centralizers.
The constraints on loading catalyst particles into a bayonet tube provided with centralizers may be summarized as follows:
breakage of the particles under the effects of falling from too great a height (typically more than 5 m) must be avoided; jamming of particles inside the loading tube must be avoided; the particles must be prevented from leaving the loading tube in groups, as experience has shown that when a group of particles leaves the loading tube simultaneously, there is a high risk of arch formation.
This set of constraints means that the method of the present invention is a method that uses “grain-by-grain” loading and which necessitates a rigorous selection of the diameter of the loading tube with respect to the dimensions of the catalyst particles.
If dmax denotes the largest dimension of a vat particle or grain, and dmin denotes the smallest dimension of said particle, it has been shown that in order to avoid phenomena of jamming when groups of particles flow out while ensuring grain-by-grain flow within the loading tube, the following conditions must be satisfied for the diameter of the loading tube Dt and the dimensions dmax and dmin of the particle:
Dt must be both greater than 1.1 times dmax and less than 2 times dmin.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 is a diagrammatic view of a device in accordance with the present invention, showing the principal characteristics thereof;
FIG. 2 is a top view showing the angular sectors and the position of each sector of the loading tube;
FIG. 3 is a diagrammatic view of the device of the present invention equipped with the optional system for extracting fine particles and braking the catalyst particles using a counter-current of gas.
BRIEF DESCRIPTION OF THE INVENTION
The present invention can be defined as a device for loading particles of catalyst into the annular space of a bayonet type tube. A bayonet tube is usually defined as being constituted by an outer tube with diameter Dext and an inner tube, concentric with the outer tube, with diameter Dint. The annular space included between the outer tube and the inner tube constitutes the catalytic annular zone to be filled with particles of catalyst.
Such bayonet tubes are typically used in reactors for steam reforming various hydrocarbon feeds, especially natural gas; they are then in the form of a plurality of 200 to 300 tubes enclosed in a shell that may be up to 15 meters in diameter.
Clearly, the device described in the present invention may be duplicated for the desired number of times in order to ensure simultaneous loading of several bayonet tubes.
The present invention is not linked to a particular shape of the catalyst particles.
In particular, the catalyst particles may have the form of small cylinders (7) that may possibly be perforated with small channels in order to increase the specific surface area of said particles.
It is only necessary to distinguish the largest dimension, denoted dmax, in the catalyst particle, and the smallest dimension, denoted dmin. The nub of the invention is the rigorous sizing of the loading tubes via which the catalyst particles are introduced into each of the sectors of the annular zone.
The diameter of the loading tubes must be just larger than the largest dimension of the catalyst particles while also being less than 2 times the smallest dimension of said particles. The term “just larger” means a value of 1.1 times the largest dimension of the particles.
In order to ensure good concentricity of the inner and outer tubes, elements termed “centralizers” connect the inner wall of the outer tube and the outer wall of the inner tube.
Said centralizers are present in a number in the range 2 to 6 per section, preferably in a number of 3 per section of reaction tube.
Said centralizers are distributed along the bayonet tube and also contribute to its rigidity, which is an important aspect of good operability of the reactor.
The loading device of the present invention can thus allow loading of catalyst particles into the annular zone of a bayonet tube the annular section of which is divided into N angular sectors by elements termed centralizers, said device comprising:
a hopper for loading catalyst particles, located outside the plurality of tubes; a set of N vibrating chutes connected to the lower portion of the hopper and to N loading tubes, each loading tube supplying one angular sector and to N loading tubes, each loading tube supplying one angular sector and having a diameter Dt of more than 1.1 times the largest dimension of the catalyst particles, and less than 2 times the smallest dimension of the catalyst particles, the length of a loading tube initially being substantially equal to the length of a bayonet tube a set of N flexible connection elements connecting each vibrating chute to a loading tube, thereby allowing an appropriate change of direction.
The term “length of the loading tube substantially equal to that of the bayonet tube” means that the length of loading tube is less than that of the bayonet tube by less than 1 meter, and preferably by less than 0.5 meter.
In general, the number of angular sectors is in the range 3 to 6; preferably, it is 3.
In a variation of the present invention, the device may be completed by a system for extracting fine particles.
In another variation of the present invention, the device may be completed by a system for braking particles intended to limit their velocity as they descend in the loading tube, generally disposed vertically or substantially vertically.
This system for braking catalyst particles may consist of cylindrical elements disposed perpendicular to the axis of said loading tube and fixed to the wall of said tube with a vertical spacing of 1 meter plus or minus 10 cm.
The term “substantially vertical” means that the bayonet tube (and thus the associated loading tube) makes an angle of plus or minus 30° with respect to the vertical.
The loading device of the invention can carry out loading at a homogeneous density over the entire length of the bayonet tubes as well as between the various bayonet tubes constituting the catalytic zone of the reactor.
The invention also pertains to the method for using the device that is described in the next paragraph.
DETAILED DESCRIPTION OF THE INVENTION
The device for loading particles of catalyst into the annular zone of a bayonet tube comprises the following elements which are described in the order in which the catalyst particles advance. The numbers refer to FIGS. 1 and 2 :
a loading hopper ( 1 ), which may be of any type known to the skilled person; a set of N vibrating chutes ( 2 ) one end of which penetrates into the lower zone of the loading hopper ( 1 ), with the other end being in communication with each loading tube ( 4 ) via flexible connection elements ( 3 ); a set of N loading tubes ( 4 ) penetrating into each angular sector which is delimited by centralizers ( 8 ), the diameter Dt of one loading tube satisfying two conditions, a) more than 1.1 times the largest dimension, of the particles to be loaded, and b) less than 2 times the smallest dimension, of the particles to be loaded.
This set may be completed by a system for extracting fine particles of catalyst ( 10 , 12 in FIG. 3 ).
In order to slow down the fall of particles of catalyst inside the loading tube, generally vertically disposed, it may be necessary to provide a braking system for said particles. As an example, it is possible to use, as a braking system, cylindrical elements of flexible material (sort of “cilia”) disposed perpendicular to the axis of said loading tube, denoted ( 9 ) in FIG. 1 , and fixed to the wall of said tube with a vertical spacing of approximately 1 meter, the spacing being variable as a function of the fragility of the catalyst to be loaded.
Another example of braking is the use of a rising stream of air created by aspiration ( 11 ), ( 12 ), or blowing the air (denoted ( 13 ), ( 14 ) in FIG. 3 ).
Regardless of the means for circulating air that is used, a filtration device ( 10 ) can be used to retain the fine particles of catalyst that may be entrained. The term “fine particles of catalyst” means fragments of particles deriving from attrition, and which have a dimension of less than 1 mm.
Any other system for slowing down the fall of the particles may clearly be envisaged and is also encompassed in the scope of the invention.
After loading the bayonet tubes, the quality of loading is verified by measuring the pressure drop (ΔP) of the catalytic bed filling the annular zone, i.e. between the inlet to the bayonet tube on the catalyst side (upper end of annular space) and the outlet from the bayonet tube (upper end of the inner tube).
The measurement of ΔP is carried out by causing a flow of air to pass through the tube loaded with catalyst. Good loading corresponds to a deviation in ΔP between two tubes of less than ±5% with respect to the mean, which ensures a homogeneous distribution of particles of catalyst between the various tubes.
The method for loading a bayonet tube consists of the following series of steps:
loading catalyst into the loading hopper; passing the grains into N vibrating chutes; “grain-by-grain” loading into the N loading tubes; shortening the loading tubes when the height of the layer of loaded particles approaches the lower end of the loading tube by a distance of less than 1 meter, and preferably less than 0.5 meter; verifying the quality of loading by measuring the pressure drop, causing air to circulate in the catalytic bed filling the annular zone, the measurement of ΔP being taken between the upper end of the annular space filled with catalyst and the upper end of the inner tube, substantially at the same level.
EXAMPLE IN ACCORDANCE WITH THE INVENTION
One Considers a steam reforming reactor intended for the production of 100000 Nm 3 /hour of synthesis gas, composed of a multiplicity of bayonet tubes, each bayonet tube being formed by a concentric inner tube and outer tube. There are 3 centralizers per section of tube, the various centralizers being aligned along the bayonet tube, and thereby defining 3 angular sections:
internal diameter of outer tube ( 5 ): Dext=150 mm; external diameter of inner tube ( 6 ): Dint=50 mm; dimension of annular space: e=50 mm; length of bayonet tube: Lb=12 m; diameter of reactor: 10 meters; number of angular sectors: N=3; number of bayonet tubes: 280.
The dimensions of the catalyst particles with a cylindrical shape were:
minimum diameter=9 mm; maximum diameter=16 mm
The loading device was constituted by:
loading hopper; number of vibrating chutes: N=3; number of loading tubes: N=3; diameter of loading tubes: Dt=18 mm; initial length of loading tube Lt=11 m silicone cylinder braking device, disposed every 50 cm.
Each loading tube was composed of an assembly of 11×1 meter sections.
When the height of the catalytic bed in the annular zone increased, the sections were lifted gradually in order to shorten the total length of the loading tube and thereby to keep the fall height for the particles below 1 meter.
The height of the fall is determined as the distance separating the upper end of the layer of particles already loaded into the annular zone and the outlet end of the loading tube.
Four loading operations, denoted 1, 2, 3 and 4, were made with the device of the invention.
The results in terms of density of the bed of catalyst (kg/m 3 ) and pressure drop (ΔP in mbar, i.e. 10 −3 bar=10 2 pascals) were as follows:
Loading operation
1
2
3
4
Mass of loaded
189
187
187
183
grains (kg)
Loading height
11850
11850
11850
11850
(mm)
Loading vol-
186
186
186
186
ume (liter)
Bed density
1017
1003
1003
981
(kg/m 3 )
Air flow rate
70
70
70
70
(m 3 /h)
ΔP (mbar)
183.2
177.7
180.3
171.2
Mean deviation
+2.86%
−0.21%
+1.22%
−3.87%
of ΔP/mean ΔP
The loading time for one tube was approximately half an hour.
The total time for loading all of the 280 tubes was 35 hours, grouping the bayonet tubes in groups of 70. Four loading devices were used in parallel.
Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The following preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.
The entire disclosure[s] of all applications, patents and publications, cited herein and of corresponding French application Ser. No. 09/04.683, filed Oct. 1, 2009 are incorporated by reference herein.
The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.
From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions. | A device and method to load particles of catalyst on the order of cm in the principal dimension into an annular zone of reaction tubes which may reach a height of more than 10 meters, while satisfying the strict conditions of homogeneity and density of loading. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a liquid crystal display (LCD) projector, and more particularly to a portable LCD projector including an optical part and a mechanical part both contained in a bag-type housing.
2. Description of the Prior Art
Various types of portable television sets are known such as a cathode-ray tube (CRT) television set having a screen of about five to six inches and, an LCD pocket television set having a screen of about three to four inches and using a back light illuminated at the rear side of a color LCD.
A typical rear projection type LCD projector is illustrated in FIG. 1 which comprises a lighting unit, an image display unit and a projection unit. The lighting unit includes a lamp 1, a reflector 2 and a condensing lens 3. The image display unit is an LCD 5 which is driven by a television circuit 4. And the projection unit includes a projection lens 6 and a rear projection type screen 7 which forms an image projected from the LCD 5 and diffracts an incident light toward a viewer side. The lighting unit is adapted to condense a light emitted from the lamp 1 and illuminate uniformly the LCD 5, and the LCD 5 is adapted to control the transmittance of light depending upon the television image by being driven by the image signals which are input from the television circuit 4.
The projection lens 6 of the projection unit is adapted to form a picture on the rear projection screen 7 by projecting a light from the LCD 5 and the rear projection screen 7 disperses the light at various angles to make the brightness of screen uniform and allows the screen to be watched at various directions.
In accordance with the prior art as discussed above, however, the portable television sets such as the small-sized CRT television and the LCD television, are limited in their screen size to five to six inches or three to four inches, so that it is unsuitable to fully enjoy the picture image; Also, the rear projection type LCD projector may have a relatively large sized screen and therefore inconvenient to carry.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide a portable LCD projector which has not only a large-sized screen but is convenient to carry.
Another object of the present invention is to provide a portable projector which is able to be used in both the rear projection type and the front projection type.
Other objects and further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. It should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
Briefly described, the present invention relates to a portable LCD projector which comprises a lighting unit for converting a light emitted from a light source into a paralled light; a liquid crystal display (LCD) for controlling a transmission amount of light emitted from the lighting unit by being driven by a television circuit; a first conversion unit for changing a path of an image which has been formed by the LCD; a projection lens for magnifying the image from the first conversion unit at a predetermined rate; a second conversion unit for reflecting the image magnified by the projection lens at a predetermined angle; a screen for forming the image reflected by the second conversion unit; and a housing for containing therein the lighting unit, LCD, first conversion unit, projection lens, second conversion unit and screen.
The rear projection screen is detachably mounted to the screen holder which is rotatably mounted to a housing and provided with a rectangular transmitting hole. Thus, when the portable LCD projector according to the present invention is used as a rear projection type, the projector may be operated under a condition that the screen is inserted in the screen holder. While in case that the projector is to be used as a front projection type, the screen is removed from the screen holder and then a front projection screen is provided at a position in front of the screen holder. Thus, a light reflected by the movable mirror passes through the transmitting hole of the screen holder and then forms an image on the front projection screen.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will become more fully understood from the detailed description given hereinbelow and the accompanying drawings which are given by way of illustration only, and thus are not limitative of the present invention, and wherein:
FIG. 1 is a view showing the configuration of a conventional rear projection type LCD projector;
FIG. 2 is a schematic sectional view showing a portable LCD projector of the present invention which is in a carrying state;
FIG. 3 is a sectional view showing the portable LCD projector of the present invention which is in an operation state; and
FIG. 4 is a partial sectional view showing the configuration of the portable LCD projector of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now in detail to the drawings for the purpose of illustrating preferred embodiments of the present invention, the portable LCD projector as shown in FIGS. 2 and 3 comprises generally an optical part and a mechanical part, both parts being contained in a bag type housing 1.
The optical part includes a projection lens 11, an LCD 12, a screen 13, an LCD mirror 16 disposed between the LCD 12 and the projection lens 11, a fixed mirror (first projection mirror) 14 disposed between the projection mirror 11 and the screen 13, and a movable mirror (second projection mirror) 15 which has a mechanical properties to be easily folded. The movable mirror 15 is, of course, in a fixed state in operation.
The LCD mirror 16 leads a light which has passed through the LCD 12 toward the projection lens 11 and the fixed mirror 14 and the movable mirror 15 convert the advancing direction of the light transmitted through the projection mirror 11 and then project the light on the screen 13. By such an arrangement, the light path suitable for a screen of about fourteen inches may be obtained within the space of the housing 1.
On the other hand, the mechanical part, in operation, allows the two projection mirrors, i.e., the fixed mirror 14 and the movable mirror 15, and the screen 13 to be maintained at an angle at which a normal operation may be carried out, while in non-use such as a carrying state, the movable mirror 15 and the screen 13 are folded on the outer casing 10 so as to be carried in a bag type.
The screen holder assembly 17 includes a screen holder 17c and screen fixing members 17a and 17b. The screen holder 17c is fixedly supported by the screen fixing members 17a and 17b and the screen 13 is detachably mounted to the screen holder 17c. That is, in a rear projection or non-use of the projector, the screen 13 is inserted in the screen holder 17c while in a front projection, the screen 13 is removed from the screen holder 17c. Also, the screen holder 17c is provided with a rectangular transmitting hole 32 which is slightly smaller than the screen 13 so as to be compatibly used in the rear projection and front projection.
The screen fixing member 17a is rotatably mounted on the upper peripheral portion of the outer casing 10 by means of a hinge 20. One end of the screen holder 17c is fixed to the screen fixing member 17a and the other end thereof is fixed to the outer screen fixing member 17b.
Rotatably coupled to the screen fixing member 17b is a mirror holder 18 having the movable mirror 15 at the inner surface thereof by means of a hinge 21. At the other end of the mirror holder 18, a pair of support pieces 23 which are inserted in a pair of hooking grooves 22 formed at the upper surface of the outer casing 10 are provided so that the movable mirror 15 may be maintained at a precise operation angle. At the upper portion of the mirror holder 18, a locker 24 is provided which is adapted to be hooked to a hooking groove 25 is formed at the outer casing 10, as shown in FIG. 4.
In addition, at both sides of the screen holder 17c and the mirror holder 18, triangular external light cutoff curtains 19 are provided which prevent the contrast from being deteriorated by an external light. The curtains 19 preferably may be made by pleated material. That is, the curtains 19 are folded between the screen 13 and the movable mirror 15 in unuse state while in an operation state, they are streched to cut off external light.
In the drawings, reference numeral 26 is a lamp, 27 a reflector, 28 a condensing lens and 29 a handle.
The portable LCD projector of the present invention operates as follows:
FIG. 2 shows the portable LCD projector which is in a non-use state in which the locker 24 is locked to the hooking groove 25 of the outer casing 10. In this state, the locker 31 is also locked to the hooking groove of the screen assembly 17b so that the screen 13 may not be exposed by the screen cover 30.
When the portable LCD projector is used as a rear projection type, the locker 24 is released from the hooking groove 25 of the outer casing 10, and then the screen 13 is rotated around the hinge 20 in counterclockwise, as shown in FIG. 3. Thereafter, the support pieces 23 of the mirror holder 18 are inserted to the hooking grooves 22 of the outer casing 10 and the locker 31 of the screen cover 30 is released from the hooking groove 33 formed at the upper portion of the screen fixing member 17b. Then the screen cover 30 is rotated around the hinge 20 in counterclockwise so that the screen 13 is exposed and the elements of the optical and mechanical parts are disposed at their operation positions.
In this state, the light emitted from the lamp 26 advances in the direction (y), as shown in FIG. 4, and is reflected at the LCD mirror 16 and then being incident upon the projection lens 11 in the direction (-x). The light which has passed through the projection lens 11 further advances in the direction (-x) and then projected on the screen 13 after being reflected at the fixed mirror 14 and the movable mirror 15. At this moment, since the screen 13 is maintained at a predetermined inclined angle, it is possible to conveniently watch the screen 13.
Although it has been described that the portable LCD projector is used as a rear projection type, the projector of the present invention may be operated for the front projection. In such case, the rear projection screen 13 should be removed from the screen holder 17c and then a separate front projection screen (not shown) is disposed at a predetermined position in front of the screen holder 17c. At this moment, a light which is reflected at the fixed mirror 14 and the movable mirror 15 passes through the transmitting hole 32 formed at the screen holder 17c, without any restriction by the screen 13 because the screen 13 has been removed from the screen holder 17c, and then projected on the front projection lens.
In this case, when the optical units which have been disposed for the rear projection are used for the front projection as they are, an inverted image is formed on the front projection screen. Thus, it is required to invert the image which is outputted from the LCD 12.
As described above in detail, the present invention provides the effect that it is convenient to carry the LCD projector even it has a relatively larger sized screen by the arrangement of the bag type housing containing therein the optical and mechanical parts. Also, it is possible to use the LCD projector of the present invention as a rear projection and a front projection as well.
Thus invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included in the scope of the following claims. | A portable liquid crystal display (LCD) projector with a bag type housing containing therein an optical part and a mechanical part which is capable of being used in both front projection type and rear projection type and enhancing the carrying performance while having a proper screen size. The projector includes a fixed mirror and a movable mirror disposed between a projection screen and a screen, and a fixed LCD mirror disposed between the LCD and the projection lens. The screen is detachably mounted to a screen holder which is movably mounted to a housing and provided with a rectangular transmitting hole and mounted to the screen holder is a mirror holder attached with the movable mirror. | 7 |
This is a division of application Ser. No. 238,466 filed Mar. 27, 1972, now abandoned.
BACKGROUND OF THE INVENTION
This invention relates to novel plastic compositions having enhanced environmental degradability.
The advent of plastics has given rise to improved methods of packaging goods. For example, polyethylene and polypropylene plastic films, bags, bottles, styrofoam cups and blister packages have the advantages of being chemically resistant, relatively unbreakable, light in weight and translucent or transparent. The increasing use of plastics in packaging applications has created a serious waste disposal problem. Burning of these plastic materials is unsatisfactory since it adds to air pollution problems.
Unlike some other packaging materials, such as paper and cardboard, plastics are not readily destroyed by the elements of nature. Thus, burying them is not an effective means of disposal, and can be expensive.
Plastics are biologically recent developments, and hence are not easily degradable by microorganisms which attack most other forms of organic matter and return them to the biological life cycle. It has been estimated that it may take millions of years for organisms to evolve which are capable of performing this function. In the meantime, plastic containers and packaging films are beginning to litter the countryside after being discarded by careless individuals.
Problems of litter and solid waste could be minimized if the rate of chemical deterioration of plastics could be enhanced. This would have the further advantage that the constituent atoms and/or stored energy in such plastics could be re-used in natural ecological processes.
The enhancement of the rate of environmental deterioration of plastics through the use of degradation-promoting additives is known in the prior art. For example, the preparation of degradable polyolefin films containing certain organic derivatives of transition metals is described in U.S. Pat. No. 3,454,510.
In most cases, the additives suggested for use as degradation-promoting agents are themselves non-polymeric in nature. The use of such additives can be complicated by their tendency to be removed from the polymer as a result of gradual vaporization, leaching, diffusion, and/or chemical destruction. Furthermore, the removal of additives under environmental conditions may lead to contamination of the air and water, hazards to wildlife, etc. Likewise, the use of such additives may detract from the useful physical properties of the plastics, and undesired degradation may occur during the preparation of polymer/additive mixtures and the fabrication of plastic articles therefrom.
The present invention is intended to avoid such difficulties through the use of polymeric degradation-promoting additives. A further objective is the minimization of solid-waste disposal problems through the development of secondary uses for recovered or off-grade plastics which are unsuitable for conventional uses.
DESCRIPTION OF THE INVENTION
In accordance with this invention, a degradable plastic material is prepared by the combination of an organic polymer and a degradation-promoting amount of a partially degraded organic polymer.
The phrase "partially degraded organic polymer," as used herein, may be defined as an organic material, which is polymeric as judged by molecular-weight measurements, which has been obtained by the partial chemical destruction of an organic polymer or copolymer. Such chemical destruction may be the result of the action of heat, light, oxygen, water, ionizing radiation, or chemical reagents, individually or in combination.
The partially degraded organic polymer may be obtained as a material recovered from solid waste, as a material degraded during polymer processing, or as the product of a separate "controlled degradation" process. In the latter case, additives and chemical reagents may be employed in order to accelerate and direct the course of the degradation process.
In general, the effectiveness of partially degraded polymers in accelerating the degradation of other polymeric materials can be attributed to the presence of degradation-promoting functional groups. In particular, oxygenated groups (e.g., carbonyl and hydroperoxide groups introduced as a result of partial oxidative degradation) serve to accelerate thermal-oxidative and/or photo-oxidative degradation processes.
The organic polymer base and the degradation-promoting polymer may be the same or different polymers.
Typical organic polymers (and copolymers) contemplated especially include polyethylene, polypropylene, poly(1-butene), poly(4-methyl-1-pentene), ethylene-propylene copolymers, ethylene- 1-butene copolymers, ethylene-1-hexene copolymers, ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers, ethylene-acrylic acid copolymers and their salts, polystyrene, polyvinyl chloride, poly(vinylidene (vinylidene chloride), polyvinyl fluoride, poly(vinylidene fluoride), polyoxymethylene, poly(ethylene oxide), poly(propylene oxide), polyvinyl alcohol, polyvinyl acetate, polyvinyl formal, polyvinyl butyral, poly(methyl acrylate) poly(ethyl acrylate), poly(caprolactam), poly(hexamethyleneadipamide), poly(ethylene terephthalate), vinyl chloride-vinyl acetate copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, cellulose acetate, cellulose propionate, cellulose acetate butyrate, ethyl cellulose, methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose. Preferred polymers include polyethylene, polypropylene, poly(4-methyl-1-pentene), polystyrene and polyvinylchloride.
It is contemplated that the degradable polymeric compositions prepared in accordance with this invention will ordinarily contain about 70 to about 99.9% by weight of the polymeric base material and about 0.1 to about 30% of the partially degraded polymeric additive.
The rate of environmental deterioration will depend upon the environmental conditions (wavelength and intensity of light, oxygen pressure, temperature, humidity, etc.); the concentration of the partially degraded polymeric additive; and/or the physical properties and chemical reactivity of the partially degraded polymeric additive and the polymeric base material. Ordinarily, the use of high concentrations of partially degraded polymeric additive will lead to a more rapid deterioration.
The novel plastic compositions of this invention can be prepared by a number of methods. A preferred method consists essentially of heating the polymeric base at a temperature below its decomposition temperature, incorporating the partially degraded polymeric additive, and mixing the ingredients so as to obtain a substantially uniform mixture. The mixture can then be molded and cooled to form a solid molded article. In the alternative, the mixture can be extruded and cooled to form a solid extrudate. Conventional plastic processing equipment can be used for melting the polymer, mixing the polymer with the additive(s) and molding or extruding the resulting mixture. Processing conditions, such as temperature, time, and pressure, will be obvious to those skilled in the art.
Another preferred process for preparing the novel plastic compositions of this invention consists essentially of blending the polymeric base and the partially degraded polymeric additive so as to obtain a substantially uniform mixture. The two materials are preferably in the form of pellets, granules or powder. Conventional plastic processing equipment can be used in the blending operation. The processing conditions will be obvious to those skilled in the art. The resulting mixture can be melted at a temperature below the decomposition temperature of the polymer and additive(s). The resulting melt can be extruded or molded and cooled to form a solid extrudate or molded article.
An alternative process for the preparation of degradable polymeric compositions involves the preparation of a solution or dispersion of the polymeric base material and the partially degraded polymeric additive in a suitable solvent. A film or coating of degradable polymeric material is then prepared by the application of such a solution or dispersion to a substrate such as glass. If desired, the dried film may be removed from the substrate and used as a film.
A coating composition containing the partially degraded polymeric additive may be applied to the surface of a plastic film, sheet, or molded article prepared from the polymeric base material. Alternatively, a composite film or three-dimensional article may be prepared by lamination of separate layers consisting essentially of the polymeric base material and the partially degraded polymeric material, respectively.
The following EXAMPLE represents one of the best embodiments contemplated by the inventors.
EXAMPLE
Unstabilized polypropylene (Profax 6401) is heated 24 hours in an air oven at 160° C. A solution of 0.2 grams of the resulting material and 9.8 grams of unstabilized polyethylene in 200 milliliters of xylene is prepared and used to cast films onto heated glass substrates. One such film, when dry, is subjected for 24 hours to the light from a 16-watt ultraviolet source emitting principally at 305 millimicrons. The infrared spectrum of the irradiated film has a substantial carbonyl peak at ca. 5.8 microns, indicative of oxidative degradation. Irradiation of a similarly prepared film of additive-free polyethylene is shown to cause negligible photo-oxidation under these conditions.
It is further contemplated that the novel degradable plastic compositions of this invention can also contain non-reactive additives. By the term "non-reactive additives" is meant a chemical additive, filler, or reinforcement commonly used in the formulation of plastic compositions which does not materially interfere with the degradation process. For example, the compositions of this invention can contain additives and processing aids, colorants, viscosity depressants, mold-release agents, emulsifiers, and slip agents. The compositions of this invention can also contain anti-oxidants, anti-static agents, and fibrous reinforcements which do not materially detract from the eventual degradation of the composition. The compositions of this invention can also contain fillers, such as barium sulphate, calcium carbonate, calcium silicate, fumed colloidal silica, glass, and clay.
Flame retardants, lubricants, plasticizers, adhesion promoters and stabilizers, such as those used to prevent thermo-oxidative decomposition can also be used. In some cases, it may be desirable to add an antioxidant or stabilizer to permit high temperature processing, even though such additive may slow the degradation process. In other cases, it may be desirable to retard degradation for a limited period of time.
It is further contemplated that films of degradable polymer, prepared in accordance with this invention, may be used as a protective and/or decorative coating for glass containers. The enhanced degradability of such coatings will facilitate their removal from used glass containers, so that the glass can be recovered for re-use. | There is disclosed the preparation of a degradable polymeric material consisting essentially of an organic polymeric base containing a degradation-promoting amount of a partially degraded organic polymer. The organic polymeric base and the degradation-promoting additive may be derived from the same or different polymers. The invention is especially useful in controlling the environmental deterioration of plastics. The rate of deterioration is a function of the environmental conditions such as light, oxygen, and temperature; the concentration of the additive; and the chemical structure(s) of both the base and the additive. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of U.S. patent application Ser. No. 09/293,188, filed Apr. 16, 1999, pending, which application is a continuation of U.S. patent application Ser. No. 09/143,289, filed on Aug. 28, 1998, titled “PLASMA TREATMENT OF AN INTERCONNECT SURFACE DURING FORMATION OF AN INTERLAYER DIELECTRIC,” now U.S. Pat. No. 6,150,257, issued Nov. 21, 2000, which is incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to semiconductor chip processing. More particularly, the present invention relates to electrically conductive interconnects covered with interlayer dielectrics. In particular, the present invention relates to electrically conductive interconnects having a passivation layer thereon that protects the interconnects such that the formation of oxide husks thereon is substantially eliminated.
BACKGROUND
[0003] In the microelectronics industry, a substrate refers to one or more semiconductor layers or structures that include active or operable portions of semiconductor devices. In the context of this document, the term “semiconductive substrate” is defined to mean any construction comprising semiconductive material, including but not limited to bulk semiconductive material such as a semiconductive wafer, either alone or in assemblies comprising other materials thereon, and semiconductive material layers, either alone or in assemblies comprising other materials. The term “substrate” refers to any supporting structure including but not limited to the semiconductive substrates described above.
[0004] Semiconductor chip processing technology involves miniaturizing a plurality of semiconductive devices and placing them side-by-side upon a wafer. As miniaturization technology progresses, it has become expedient to stack semiconductive devices in order to retain a small chip footprint. It is also necessary to connect stacked devices by way of formation of an interconnect corridor and by filling of the interconnect corridor with electrically conductive material such as a tungsten stud. Metallization lines are formed that make electrical connection to the tungsten stud. These metallization lines need to be electrically isolated from semiconductive devices that are formed above an existing layer of semiconductive devices. To this end, an interlayer dielectric (ILD) such as an oxide or nitride is formed.
[0005] FIG. 1 is an elevational cross-section view of a semiconductor structure 10 that depicts interconnects 12 within a dielectric layer 14 . Semiconductor structure 10 has an upper surface 16 upon which an interlayer dielectric (ILD) layer 18 has been formed. The left half of FIG. 1 depicts an initial effect of formation of ILD layer 18 according to the prior art. It can be seen that the portion of interconnect 12 that was exposed as part of upper surface 16 of semiconductor structure 10 has formed an oxide husk 20 upon interconnect 12 . Oxide husk 20 is formed either after planarization to form upper surface 16 , such as by chemical-mechanical planarization (CMP) or during the deposition of ILD layer 18 . Where interconnect 12 is a tungsten plug, oxide husk 20 forms into tungsten oxide (WO 3 ).
[0006] Further processing of semiconductor structure 10 , including thermal processing, causes complications that arise in the prior art. The right half of FIG. 1 depicts one prior art problem. It can be seen that, due to a large stress between oxide husk 20 and interconnect 12 , oxide husk 20 has delaminated from interconnect 12 due to adhesion failure, and pushed upwardly to form a void 22 immediately above interconnect 12 . Void 22 causes planarity problems and can also lead to underetched trenches prior to metal fill. The delamination of oxide husk 20 is an indication of a relatively thick oxide over interconnect 12 . The thickness of oxide husk 20 can range from about 10 Å to about 500 Å. Oxide husk 20 needs to be removed prior to deposition of a metal line. The presence of void 22 causes a prominence in the ILD topology. The prominence can lead to underetched trenches prior to metal fill, resulting in the metal line not making sufficient electrical contact with interconnect 12 . In addition, the prominence caused by the formation of void 22 can be formed during ILD deposition. Additionally, the prominence formed due to void 22 could cause some imaging problems because of a departure from substantial planarity of the upper surface of the ILD.
[0007] The delamination of oxide husk 20 from upper surface 16 immediately above interconnect 12 creates significant yield problems and device failure both during device testing and in the field.
[0008] What is needed in the art is a method of overcoming the prior art problems. What is also needed in the art is a method of forming an ILD layer without the formation of an oxide husk and the subsequent formation of a void between the top of the interconnect and the ILD layer. What is needed in the part is a method of preventing or reducing the oxidation of the upper surface of a metallic interconnect during the formation of an interlayer dielectric.
SUMMARY OF THE INVENTION
[0009] The present invention relates to the formation of an ILD layer while preventing or reducing oxidation of the upper surface of an electrically conductive interconnect or contact. Prevention or reduction of oxidation of the upper surface of an interconnect or contact is achieved according present invention by passivating the exposed upper surface of the interconnect or contact prior to formation of the ILD. It is to be understood that “interconnect” and “contact” can be interchangeable in the inventive method and structures.
[0010] In order to avoid the oxidation of an upper surface of an interconnect during the formation of an ILD layer, an in situ passivation of the upper surface of the interconnect, immediately prior to or simultaneously with the formation of the ILD layer, avoids the problems of the prior art.
[0011] A preferred embodiment of the present invention comprises providing a semiconductor structure including a dielectric layer. Following the formation of the dielectric layer, a depression is formed in the dielectric layer. The depression terminates at an electrically conductive structure therebeneath. The depression is then filled with an interconnect that is composed of an electrically conductive material, such as a refractory metal, and preferably tungsten. After filling of the depression with the interconnect, an upper surface of the interconnect and dielectric layer is formed by a method such as chemical-mechanical planarization (CMP).
[0012] Following the formation of the upper surface, a chemical composition is reacted with at least one monolayer of the upper surface of the interconnect to form a chemical compound having a higher resistance to oxidation than the interconnect.
[0013] Preferably, the chemical composition will be a nitrogen-containing chemical compound such as ammonia, NH 3 . Where the interconnect is a refractory metal, such as tungsten, the at least one monolayer forms a tungsten nitride-type composition or adsorbed complex. Following formation of the at least one monolayer upon the upper surface of the interconnect, formation of the ILD layer may be carried out by such methods as a deposition by the decomposition of tetra ethyl ortho silicate (TEOS), or by chemical vapor deposition (CVD) of oxides, nitrides, carbides, and the like.
[0014] In order to form an ILD layer using lower processing temperatures, it is preferred that a CVD be carried out under plasma-enhanced (PE) conditions, i.e., PECVD.
[0015] Formation of the ILD layer may be carried out in a manner that introduces materials to form the ILD layer simultaneously with the introduction of the ammonia plasma to create a passivation layer upon the upper surface of the interconnect.
[0016] Next, formation of the ILD layer with substantially like materials is carried out under conditions where the ILD layer substantially absorbs the passivation layer and the passivation layer is sufficiently thick to resist substantial formation of the oxide husk.
[0017] Alternative compositions to ammonia may be used during plasma treatment of the upper surface of the interconnect. For example, nitrogen-containing compositions that are preferred for the inventive method include ammonia, diatomic nitrogen, nitrogen-containing silane, and the like.
[0018] These and other features of the present invention will become more fully apparent from the following description and appended claims, or may be learned by the practice of the invention as set forth hereinafter.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] In order to illustrate the manner in which the above-recited and other advantages of the invention are obtained, a more particular description of the invention briefly described above will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. Understanding that these drawings depict only typical embodiments of the invention and are not therefore to be considered limiting of its scope, the invention will be described and explained with additional specificity and detail through the use of the accompanying drawings in which:
[0020] FIG. 1 is an elevational cross-section view of a semiconductor structure comprising a dielectric layer and a metallic interconnect according to the prior art. It can be seen in FIG. 1 that two stages of processing are illustrated, whereby an oxide husk upon the interconnect expands to create a void and a substantially non-planar topology for subsequently deposited layers.
[0021] FIG. 2 is an elevational cross-section view of a semiconductor structure being manufacturing according to the inventive method, where a contact corridor has been opened in a dielectric layer and a liner layer has been deposited upon the dielectric layer and within the contact corridor.
[0022] FIG. 3 is an elevational cross-section view of the semiconductor structure depicted in FIG. 2 after further processing, wherein a metal nitride layer has been formed upon the liner layer, an electrically conductive stud or interconnect has been filled into the depression, and wherein an upper surface has been created by a technique such as planarization. The upper surface includes both the dielectric layer and the interconnect, and wherein a passivation layer has been formed upon the upper surface.
[0023] FIG. 4 is an elevational cross-section view of the semiconductor structure depicted in FIG. 3 after further processing, wherein an ILD layer has been formed upon the upper surface according to the inventing methods such that the passivation layer has substantially protected the electrically conductive stud such that oxidation has been substantially resisted.
[0024] FIG. 5 is an elevational cross-section view of the semiconductor structure depicted in FIG. 4 after further processing, wherein a second depression has been formed into the ILD layer according to damascene technology in order to allow a metallization trench to be formed, or an upper level contact to be electrically connected to the interconnect that is beneath the ILD layer.
DETAILED DESCRIPTION OF THE INVENTION
[0025] Reference will now be made to the drawings wherein like structures will be provided with like reference designations. It is to be understood that the drawings are diagrammatic and schematic representations of the embodiment of the present invention and are not drawn to scale.
[0026] The present invention relates to the formation of an ILD layer while preventing or reducing oxidation of the upper surface of an interconnect or contact stud. Prevention or reduction of oxidation of the upper surface of an interconnect is achieved according to the present invention by passivating the exposed upper surface of the interconnect prior to formation of the ILD.
[0027] In reference to FIG. 2 , prevention or reduction of the likelihood of oxidation of upper surface 16 of interconnect 12 is accomplished during the formation of ILD layer 18 . This is carried out by an in situ passivation of upper surface 16 of interconnect 12 , immediately prior to or simultaneously with the formation of ILD layer 18 , which avoids the problems of the prior art.
[0028] A preferred embodiment of the present invention, illustrated beginning at FIG. 2 , comprises providing semiconductor structure 10 including a dielectric layer 14 . Following the formation of dielectric layer 14 , a depression 26 is formed in dielectric layer 14 so as to terminate at an electrically conductive structure therebeneath such as a substrate 24 . Depression 26 is then filled with an interconnect 12 as seen in FIG. 3 , composed of an electrically conductive material such as a refractory metal. Interconnect 12 can be a tungsten stud or the like. After filling of depression 26 with an electrically conductive material, upper surface 16 of interconnect 12 and upper surface 16 of dielectric layer 14 is formed by a method such as CMP as illustrated in FIG. 3 .
[0029] Following the formation of upper surface 16 , a chemical composition is reacted with at least one monolayer of upper surface 16 of interconnect 12 to form a chemical compound having a higher resistance to oxidation than interconnect 12 .
[0030] The chemical compound is provided in an amount sufficient to substantially chemically cover upper surface 16 of interconnect 12 in order to chemically protect approximately the first 1-1,000 atomic lattice layers thereof. The chemical compound may be a nitride form of the metal of which interconnect 12 is composed. Where ammonia, a hydrated nitrogen compound or the like is used, a chemical structure such as M-N-H x forms, where M represents the metal of which interconnect 12 is composed.
[0031] The chemical compound may be, by way of non-limiting example, the nitrogen-containing chemical compound such as ammonia that has been adsorbed onto upper surface 16 of interconnect 12 sufficiently to substantially chemically cover or ‘blind off’ substantially any chemically reactive portion of upper surface 16 of interconnect 12 during formation of ILD layer 18 . Use of preferred chemical compounds that arc to be matched with specific materials comprising interconnect 12 can be selected by one of ordinary skill in the art using such data and equations as Langmuir's monolayer adsorption isotherm or those also taught by Brunauer. Emmett, or Teller. Of interest to selection of a particular chemical compound in connection with a preferred material for interconnect 12 , will be any one of the five types of adsorption isotherms as classified by Brunauer. 1 1 O. Hougen et al., Chemical Process Principles 2 nd Ed ., Chapter 10: Adsorption. John Wiley and Sons, Inc. (1954).
[0032] It is of interest in the present invention that the formation of a passivation layer 32 , as seen in FIG. 3 , substantially protects upper surface 16 of interconnect 12 from oxidation to a degree wherein the formation of oxide husk 20 and void 22 are substantially eliminated. Passivation layer 32 may be achieved by formation of a chemical compound upon upper surface 16 of interconnected 12 by a chemical reaction with approximately the first 1-1,000 atomic lattice layers of interconnect 12 or it may be achieved by adsorption onto upper surface 16 of interconnect 12 according to any of the aforementioned types as taught by Brunauer.
[0033] Preferably, the chemical composition will be a nitrogen-containing chemical compound such as ammonia, NH 3 . Where interconnect 12 is a tungsten stud, the at least one monolayer reacts to form a tungsten nitride-type composition or adsorbed complex upon the at least one monolayer. Following reaction with the at least one monolayer of upper surface 16 of interconnect 12 , formation of ILD layer 18 may be carried out by various methods. One method is deposition by the decomposition of tetra ethyl ortho silicate (TEOS), or by CVD of oxides, nitrides, carbides, and the like.
[0034] In order to form ILD layer 18 using lower processing temperatures, it is preferred that a CVD be carried out under plasma-enhanced conditions, i.e., PECVD. According to the inventive method, PECVD temperatures are used in a temperature range from about 100° C. to about 600° C. Preferably, the processing temperature will be in a range from about 150° C. to about 500° C., more preferably from about 200° C. to about 450° C., and most preferably 300° C. to about 400° C.
[0035] According to the present invention, a first example is set forth below. Following the formation of dielectric layer 14 , as illustrated in FIG. 2 , depression 26 such as a contact corridor is formation therein, exposing semiconductor substrate 24 that may be, by way of non-limiting example, a metallization line. Following the exposure of semiconductor substrate 24 , a titanium liner layer 28 or the like is formed within depression 26 . Subsequently, a titanium nitride layer 30 or the like is formed upon titanium liner layer 28 . Titanium nitride layer 30 may be formed by thermal nitridation of a portion of titanium liner layer 28 , by deposition of titanium nitride thereupon, or by a combination thereof.
[0036] Interconnect 12 is next formed within depression 26 . A preferred material for interconnect 12 is tungsten or the like. Tungsten or the like may be formed within depression 26 by CVD, PECVD, or by physical vapor deposition (PVD).
[0037] Upper surface 16 as seen in FIG. 3 , may be formed by such methods as CMP or an anisotropic etchback that has an etch recipe selectivity that is substantially the same for interconnect 12 as for dielectric layer 14 . By “substantially the same,” it is meant that selectivity favors leaving dielectric layer 14 , and favors it over interconnect 12 in a range from about 1.5:1, preferably about 1.2:1, more preferably 1.1:1, and most preferably 1.05:1.
[0038] Passivation of upper surface 16 of interconnect 12 is next carried out by placing semiconductor structure 10 within a tool such as a PECVD chamber and introducing and striking an ammonia plasma or the like therein. Treatment temperatures, as set forth above, are imposed upon semiconductor structure 10 . The plasma treats upper surface 16 for a time treatment in a range from about 1 to about 60 seconds, preferably from about 5 to about 45 seconds, more preferably from about 20 to about 40 seconds, and most preferably for about 30 seconds.
[0039] Formation of ILD layer 18 , as illustrated in FIG. 4 , may be carried out in a manner that introduces materials to form ILD layer 18 simultaneously with the introduction of the ammonia plasma to create a passivation layer 32 upon upper surface 16 of interconnect 12 . Alternatively, after the formation of passivation layer 32 has been substantially accomplished, the deposition tool may be substantially evacuated of the ammonia plasma, and dielectric precursor materials may then be introduced to the deposition tool to form ILD layer 18 . Other materials may be used to form passivation layer 32 besides ammonia. For example, diatomic nitrogen or a nitrogen-containing silane may be used. The specific material that may be used will depend upon the particular application.
[0040] Next, formation of ILD layer 18 with substantially like materials is carried out under conditions where ILD layer 18 substantially absorbs passivation layer 32 and/or passivation layer 32 is sufficiently thick to resist substantial formation of oxide husk 20 . In this embodiment, it is preferred by way of non-limiting example that both passivation layer 32 be formed using NH 3 and ILD layer 18 be formed in a deposition by decomposition of TEOS. Other materials, however, may be chosen.
[0041] Completion of this example is carried out by the formation of second depression 34 in ILD layer 18 . Accordingly, a masking layer is patterned upon upper surface 36 of ILD layer 18 and an anisotropic etch is carried out to form second depression 34 . The etch recipe is selective to interconnect 12 as well as titanium liner layer 28 , titanium nitride layer 30 , and optionally to dielectric layer 14 .
[0042] Where formation of passivation layer 32 is carried out at least in part by adsorption, and where ammonia is used by way of non-limiting example, an ammonia compound and its derivatives are substantially adsorbed upon upper surface 16 of interconnect 12 . By “substantially adsorbed” it is meant that passivation layer 32 does not volatilize during the time required to form ILD layer 18 . This means that volatilization is prevented to an extent that passivation layer 32 resists formation of oxide husk 20 , or a portion thereof. Of primary interest in the present invention is the achievement of an embodiment whereby passivation layer 32 sufficiently protects upper surface 16 of interconnect 12 such that during the formation of ILD layer 18 , ILD layer sufficiently adheres to upper surface 16 of interconnect 12 without causing structural failure as that experienced in the prior art.
[0043] Additionally and preferably, any component of passivation layer 32 that volatilizes during formation of ILD layer 18 will be soluble in the materials that form ILD layer 18 such that no immiscible gas bubbles form from volatilized materials of passivation layer 32 .
[0044] A second example of the inventive method is set forth below. Semiconductor structure 10 includes dielectric layer 14 , made of borophosphosilicate glass (BPSG). Dielectric layer 14 rests upon substrate 24 . In this example, substrate 24 can be an electrically conductive film that is typically used to wire semiconductive devices.
[0045] Following the formation of dielectric layer 14 , depression 26 is formed by an anisotropic dry etch that stops on substrate 24 . The anisotropic dry etch may include such techniques as ion beam milling or an etch recipe that mobilizes a portion of the masking layer such that the masking layer redeposits upon the sidewalls of depression 26 while it is being formed, thereby forming a substantially anisotropic etch.
[0046] Following the formation of depression 26 , titanium liner layer 28 is deposited upon dielectric layer 14 and substrate 24 preferably by PECVD. Titanium liner layer 28 is then partially treated in a thermal nitride environment in order to grow titanium nitride layer 30 thereupon. Although titanium nitride layer 30 is grown by thermal combination and conversion of a portion of the titanium in titanium liner layer 28 into titanium nitride layer 30 , titanium nitride layer 30 may alternatively be formed by deposition of titanium nitride by such techniques as PVD, PECVD, CVD, and the like.
[0047] Following the formation of titanium nitride layer 30 , interconnect 12 is formed by deposition of tungsten into depression 26 . The deposition of tungsten into depression 26 in order to form interconnect 12 may be facilitated by the presence of titanium nitride layer 30 and titanium liner layer 28 . Where the formation of interconnect 12 is formed by force-filling of tungsten into depression 26 , the presence of titanium nitride layer 30 and titanium liner layer 28 facilitate slippage of the tungsten material along the region of what will become upper surface 16 and into depression 26 so as to fill depression 26 .
[0048] Following the filling of depression 26 with tungsten or the like in order to form interconnect 12 , all tungsten that is not within depression 26 is removed by a technique such as CMP. Because CMP itself may form oxide husk 20 , upper surface 16 , particularly that portion of upper surface 16 that comprises interconnect 12 , may need to be cleaned by such techniques as an interconnect oxide etch that is selective to dielectric layer 14 and unoxidized portions of interconnect 12 .
[0049] Following the cleaning of upper surface 16 , semiconductor structure 10 is placed within a deposition tool and an ammonia plasma is struck therein. Alternatively, the cleaning of upper surface 16 may be carried out within the same deposition tool where the ammonia plasma is struck. Additionally, the cleaning of upper surface 16 may be carried out within a cluster tool previous to in situ transfer of semiconductor structure 10 into the deposition tool. The temperature of semiconductor structure 10 during this stage of the inventive method is in a range substantially the same as in the previous example. Preferably, the treatment time to form passivation layer 32 is less than about 30 seconds. According to this second example, a preferred composition of passivation layer 32 comprises nitrogen that has been adsorbed upon upper surface 16 of interconnect 12 according to Brunauer's Type V adsorption. As a preferred alternative embodiment, upper surface 16 of interconnect 12 is first treated in a nitrogen atmosphere at a temperature sufficient to create tungsten nitride and then under conditions sufficient to create Type V adsorption of several layers of nitrogen compounds upon the tungsten nitride. By several layers of nitrogen compounds, it is understood that the overall composite thickness of passivation layer 32 is about 50 Å, preferably about 20 Å, more preferably about 10 Å, and most preferably about 5 Å.
[0050] Another example is set forth below. Processing is carried out as set forth in previous examples. The formation of passivation layer 32 is carried out in situ with the formation of ILD layer 18 . After an optional cleaning of upper surface 16 , semiconductor structure 10 , within a deposition tool, is fed with a mixture of ammonia and silane or the like. At the beginning of this step of the inventive process, the mixture comprises an ammonia rich feed such that initially passivation layer 32 begins to form upon upper surface 16 .
[0051] The removal of ammonia from the mixture may be carried out incrementally. For example, the elimination of ammonia from the mixture may be initiated by decreasing the ammonia portion of the mixture by a preferred percentage of the entire amount of ammonia over a period of time. Specifically, the amount of ammonia may be decreased every five seconds by about 5%, such that after about 100 seconds, the amount of ammonia in the feed mixture is reduced to about zero. Alternatively the amount of ammonia may be decreased every five seconds by 10%, such that after about one minute, the amount of ammonia in the feed mixture is reduced to about zero. Alternatively, the amount of ammonia may be decreased by about 25% every five seconds such that after about twenty seconds, the amount of ammonia in the feed mixture has been reduced to about zero. Additionally, the amount of ammonia may be decreased by 50% every five seconds such that after about ten seconds, the amount of ammonia in the feed mixture is reduced to about zero. Finally, the amount of ammonia in the feed mixture may be reduced from 100% to about zero after any five-second time increment in a single step.
[0052] As an alternative embodiment and in connection with the reduction of the amount of ammonia in the mixture, processing conditions may be altered from conditions that are less likely to cause formation to oxide husk 20 to conditions that are more likely. For example, processing temperatures sufficient to form passivation layer 32 may be initiated with an ammonia-rich mixture under conditions not likely to cause formation of oxide husk 20 . As the amount of ammonia in the mixture is reduced, processing temperatures may be increased proportionally under conditions that are more likely to cause formation of oxide husk 20 than under conditions previously established when the amount of ammonia in the mixture is greater. The initial formation of some of passivation layer 32 , however, resists the formation of oxide husk 20 . Preferably, the processing temperature will be the same as the deposition temperature for ILD layer 18 .
[0053] Following the formation of passivation layer 32 , upper surface 16 is covered with ILD layer 18 in situ by a method as set forth above. During the deposition of ILD layer 18 , passivation layer 32 protects upper surface 16 of interconnect 12 and prevents the formation of oxide husk 20 . As a preferred alternative embodiment of the present invention, the materials comprising passivation layer 32 may react with ILD layer 18 material without causing unwanted oxidation of upper surface 16 of interconnect 12 . In this preferred alternative embodiment, the materials comprising passivation layer 32 and ILD layer 18 will interact to form a new compound that will have a lower stress than that of oxide husk 20 .
[0054] Alternative compositions to ammonia may be used during plasma treatment of upper surface 16 of interconnect 12 . For example, nitrogen-containing compositions that are preferred for the inventive method include ammonia, diatomic nitrogen, nitrogen-containing silane, and the like.
[0055] FIG. 4 illustrates further processing of semiconductor structure 10 as depicted in FIG. 3 . It can be seen that ILD layer 18 has been formed upon upper surface 16 of semiconductor 10 according to the inventive method. The presence of passivation layer 32 has prevented formation on oxide husk according to an object of the invention. It can be appreciated that passivation layer 32 may form exclusively upon interconnect 12 and alternatively onto titanium liner layer 28 and titanium nitride layer 30 . This means that passivation layer 32 may not substantially form upon upper surface 16 over dielectric layer 14 due to incompatible reaction chemistry that prevents any type of reactive material to form.
[0056] Following the formation of ILD layer 18 , further processing is carried out as illustrated in FIG. 5 . Second depression 34 is formed into ILD layer 18 by patterning and etching thereof. In a damascene process such as that illustrated in FIG. 5 , second depression 34 is formed substantially above interconnect 12 . Second depression 34 may be, by way of non-limiting example, a wiring trench such that metallization within second depression 34 would run in and out of the plane of FIG. 5 . Additionally, second depression 34 may be a contact corridor such that metallization would run left to right, substantially within the plane of FIG. 5 along the upper surface 36 of ILD layer 18 and filled into second depression 34 such that a metallization line with a contact is formed, whereby the contact is in electrical communication with interconnect 12 .
[0057] The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The described embodiments are to be considered in all respects only as illustrative and not restrictive. The scope of the invention is, therefore, indicated by the appended claims and their combination in whole or in part rather than by the foregoing description. All changes that come within the meaning and range of equivalency of the claims are to be embraced within their scope. | The present invention relates to metallic interconnect having an interlayer dielectric thereover, the metallic interconnect having an upper surface substantially free from oxidation. The metallic interconnect may have an exposed upper surface thereon that is passivated by a nitrogen containing compound. | 7 |
This is a division of application Ser. No. 669,434 filed Mar. 22, 1976, now abandoned.
BACKGROUND OF THE INVENTION
During the fabrication of rubber articles, it is common for unvulcanized calendered sheets to be laminated to obtain the desired structural configuration. This technique of building up of layers of uncured elastomer is used extensively in the tire building industry, but also finds utility in the manufacture of other rubber articles such as mechanical goods and hoses. In order that the unvulcanized composites have the necessary mechanical stability toward handling and storage, the elastomeric materials must have sufficient tack so that the desired configuration is retained through the vulcanization step. This tack is the ability of unvulcanized elastomer to adhere to itself or to another elastomer which also has tack. This adhesive property, known as "building tack" plays an important role in the production of rubber goods. In the manufacture of tires, "building tack" holds the innerliner, beads, plys, sidewalls and tread together prior to vulcanization.
Natural rubber has the advantage of having sufficient tack without tackifying resins being added. However, synthetic rubbers lack this building tack, and the use of resinous modifiers is necessary to obtain the tack required for fabrication. It is not uncommon, however, to add tackifiers to natural rubber or to blends of natural and synthetic compounds to aid in tack retention during storage of calendered unvulcanized stock. Tackifiers also provide secondary benefits by reducing compound viscosity and also by functioning as plasticisers.
A number of different types of materials are utilized as rubber tackifiers. These include various hydrocarbon resins made from feedstocks derived principally from petroleum cracking and coal tar operations. Aliphatic and aromatic type hydrocarbon resins are produced primarily from petroleum derived streams. While coumarone-indene resins are coal tar derived, similar resins are also made from petroleum sources. Polyterpenes, terpene phenolics, rosin and rosin derivatives, alkylphenol-aldehyde resins, alkylphenol acetylene resins, natural rubber and reclaimed rubber are also utilized as rubber tackifiers.
The hydrocarbon resins are in general less expensive than are the phenolics, but require the use of up to three times the amount to give equivalent tack with tack retention being adversely affected. Since tackifiers which remain in the fabricated rubber article can tend to detract from the properties of the rubber, phenolics are often advantageously used because of the lower level required. However, phenolic tackifiers do tend to decrease the adhesion of the rubber to wire or other reinforcing fibers. For this reason, hydrocarbon resins are sometimes used, even though higher percentages are required, when adhesion of the rubber to reinforcing materials is critical. This invention provides phenolic tackifiers having desirable efficiency with no adverse effect on the adhesion of the rubber to the reinforcing element.
SUMMARY OF THE INVENTION
This invention concerns a tackifier for unvulcanized elastomers comprising an alkylphenol-formaldehyde condensation product having aminomethylene groups on the phenolic ring. These compounds are prepared by the reaction of the corresponding alkylphenol-formaldehyde resin containing terminal methylol groups with di-2-hydroxyalkylamine or morpholine, or by the reaction of an alkylphenol-formaldehyde novolac with di-2-hydoxyalkylamine or morpholine in the presence of formaldehyde, or by the reaction of an alkylphenol with formaldehyde and morpholine or di-2-hydroxyalkylamine.
These compounds can also be prepared by the reaction of the corresponding alkylphenol-formaldehyde product with a N-methylol-dialkanol amine.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Phenol-formaldehyde resins normally used for imparting tack to elastomers are of the oil soluble, non-heat reactive type, prepared by the acid catalyzed reaction of a para-substituted alkyl phenol with formaldehyde. The structure of such a polymer is believed to approximate that shown in FIG. I. ##STR1##
The compatability of the resin is dramatically affected by the molecular weight (value of X) and by the R group in the para-position. These nonreactive polymers remain relatively unchanged at vulcanization temperatures.
Heat reactive alkylphenol-formaldehyde resins, on the other hand, tend to polymerize further and can lead to agglomerations of brittle thermoset polymers, resulting in a stiffening of the rubber with accompanying disadvantageous effect on modulus and tensile strength. These heat reactive polymers have structures approximately shown in FIG. II. ##STR2## We have found that the polymers of FIG. II, or the polymers of FIG. I when heated with additional formaldehyde to form terminal methylol groups, can be converted to aminomethylene derivatives by reaction with either morpholine or di-2-hydroxyalkylamines. FIG. III shows the reaction sequence starting with the alkylphenolic polymer of FIG. I. FIG. IV shows the reaction sequence starting with the alkylphenolic polymer of FIG. II. The reaction of primary and secondary amines with formaldehyde and active hydrogen compounds (the Mannich reaction) has been widely studied (Organic Reactions, Wiley, Vol. 1, Chap. 10, p. 303). This invention is concerned with the Mannich reaction only as it applies to phenols, (specifically to p-alkyl phenols) and morpholine or di-2-hydroxyalkylamines. U.S. Pat. Nos. 2,040,039 and 2,040,040 disclose the ease of the condensation of alkylated phenol, formaldehyde and morpholine to form the corresponding morpholinomethylenephenols. U.S. Pat. No. 3,001,999 discloses the reaction of p-alkylphenol with formaldehyde and amines, including morpholine. U.S. Pat. Nos. 3,173,952 and 2,997,455 disclose the aminoalkylation of dialkylphenols; German Pat. No. 2,320,526 discloses aminoalkylation using diethanolamine.
We have found that aminomethylene terminated alkylphenols and polymers thereof, when the amine group is morpholine or a diethanolamine, will impart good tack properties to uncured rubber and, most important, provide good tack retention and also not diminish, and will usually enhance, the adhesion of the rubber to the reinforcing elements.
Tackifiers employed according to the present invention when the amine group is a dialkanol amine can be represented by the formula: ##STR3## where
R is alkyl
R 1 is CHR 3 -- N -- (CH 3 --CHOHR 3 ) 2 wherein R 3 is alkyl or hydrogen,
R 2 is R 1 or a mixture of R 1 with H or - CHR 3 OH, or both, provided that when R 2 is a mixture, R 1 is the predominant constituent of the mixture,
and where m plus n is at least 1.
The phenolic component for the compounds of this invention is a difunctional hydroxybenzene, having an alkyl substituent in the para position which contains 1-24 carbon atoms, preferably 4-12 carbon atoms. Phenols with additional substituents in the meta position are operable, but are not preferred. The alkylation procedure used to prepare the alkyl phenols is usually carried out under acid catalysts with equimolecular amounts of phenol and the alkylating agent, but normally a portion (2-5%) of the alkylation takes place in the ortho position without deleterious effect on the performance of the tackifier. The presence of a small amount of dialkylphenol, obtained by use of greater than stoichiometric amount of alkylating agent, has been found in some cases to lead to higher adhesion and tack values than expected. Typical alkylating agents are diisobutylene (octylphenol) tripopylene (nonylphenol) and tetrapropylene (dedecylphenol). The amines used to prepare the tackifier resin of this invention are morpholine and amines which can be dehydrated to morpholine, such as diethanolamine and di-2-hydroxy propylamine.
The molar ratio alkylphenol formaldehyde/amine can vary widely. At one end of the spectrum would be 2,6-diaminomethylene-4-alkylphenol with a molar ratio of 1/2/2. At the other extreme would be a ratio of alkylphenol/formaldehyde/amine of 20/28/2. The ratio selected depends, among other factors, on (1) the physical properties of the resin which are desired for easiest handling of the resin and the tackified rubber (2) the melting point desired and (3) the cost limitations. Thus, although fluid compositions are effective, we have found that preferred tackifiers have softening points between 85° and 135° C., and most preferably between 95° and 120° C. The reaction conditions for the phenol-formaldehyde condensation will also affect the ratio, since basic conditions will tend to increase the amount of benzylic ether linkages, thus increasing the formaldehyde required. This invention includes all these p-alkylphenol-formaldehyde condensation products having terminal morpholinomethylene groups, when such materials are used to improve tack of uncured rubber and to maintain the adhesive strength of the rubber-reinforced fiber bond. A typical rubber composition employing a tackifying compound of the type used according to the present invention includes brass coated steel, polyester or poly aromatic amide reinforcing fibers and the vulcanization product of uncured natural or synthetic rubber or their mixtures, extender oil, carbon black, curative agents and from 2 - 5 parts per hundred parts of rubber of a tackifying compound of the type employed according to the present invention.
Table I shows the various resins prepared and evaluated. Examples 1 through 4 are standard types of tackifiers commercially available. Examples 5-7 have been modified with polyamines, giving resins which have not shown significant improvement in adhesion, and are deleterious to tack retention. Examples 8-14 show the preparation of compounds of this invention, based on morpholine and diethanolamine. The procedures A-E listed in Table I are as follows:
Procedure A.
The phenolic component and formaldehyde (50% aqueous) and acid catalyst were charged simultaneously to a reaction vessel and reacted at 100° C. After the prescribed reaction time, the product was vacuum dehydrated to the desired softening point.
Procedure B.
The phenolic component, acid catalyst and azeotroping solvent were heated at least to the boiling point of the solvent, and aqueous formaldehyde was added incrementally while continually azeotropically removing water. Solvent was removed by vacuum distillation when the condensation was complete.
Procedure C.
The phenolic component in an azeotroping solvent was heated until the phenolic component dissolved. The amine component was added slowly so that the exotherm of dissolution did not cause the temperature to exceed 130° C. In these cases (Examples 8-11, 13, 14) where the amine was morpholine, 2-10% of triethylamine (TEA) catalyst (based on morpholine and phenol) was used. The formaldehyde (50% aqueous) was then added either as one charge (Examples 1, 3, 8, 10, 13, 14) or intermittantly (Examples 2, 5, 7, 11, 12, 15. When added as one charge, the reaction was run at full reflux, and the solvent and water were removed at the completion of the reaction by vacuum distillation. When added incrementally, the water was continually removed azeotropically over the time of formaldehyde addition.
Procedure D
Resin of Example 2 (octyl phenol novolac) was dissolved in sufficient toluene to make an 80% solids solution, heated to 110° C., and the secondary amine was added in one charge (TEA catalyst was added when morpholine was used). The temperature was raised to 120° C., and formaldehyde was added incrementally while continually azeotroping the water. The solvent was then removed by vacuum distillation.
Procedure E
Dimethylol octylphenol was prepared by the base (lithium hydroxide 93% and TEA 4%) catalyzed condensation of octylphenol (1 mole) with 50% aqueous formaldehyde (2 moles). The dimethyloctylphenol product was dissolved in toluene/benzene at 65% solids. Morpholine was added in one charge, and the reaction mass was refluxed to completion and vacumn dehydrated to the desired softening point and methylol content of less than 1%. This value for methylol content includes methylol groups and benzylic ether bridges.
Table I__________________________________________________________________________ Overall Time Mole Ratio for Catalyst phenolic/CH.sub.2 O/ CH.sub.2 O Level SofteningExampleProcedure R.sup.8 amine Amine Addition TEA Point.sup.9__________________________________________________________________________1. A octyl.sup.1 1/0.9/0 -- -- 85°-105° C.2. B octyl 1/0.95/0 -- 4 hrs. 110°-130° C.3. B dodecyl.sup.2 1/1.25/0 -- 5 hrs. 95°-115° C.4. Resin of Example 1 plus 25% pentaerythritol ester of rosin acids5. C t-butyl 1/1.15/0.25 TETA.sup.4 3 hrs. 113.5° C.6. C nonyl 1/1.35/0.25 TETA 3 hrs. 106° C.7. C t-butyl.sup.3 1/2.3/0.5 EDA.sup.5 3 hrs. 99° C.8. C H 1/3.5/1 Morpholine -- 5% 96° C.9. C t-butyl 1/3.2/1 Morpholine -- 10% paste10. C octyl.sup.6 1/2.3/1.1 Morpholine -- 9% liquid11. D octyl 1/1.2/0.23 Morpholine 20 min. 3% 104° C.12. D octyl 1/1.2/0.23 DEA.sup.7 25 min. -- 151° C.13. E octyl 1/2/0.66 Morpholine -- 4 93° C.14. E octyl.sup.6 1/1.7/0.67 Morpholine -- 4 82° C.15. C octyl 1/2/2 Morpholine 100 min. 4% liquid__________________________________________________________________________ .sup.1 From the alkylation of phenol with .sup.2 From the alkylation of phenol with .sup.3 From the alkylation of phenol with .sup.4 Triethylene tetramine .sup.5 Ethylenediamine .sup.6 The phenolic was prepared by alkylation of phenol with diisobutylene at a molar ratio of olefin to phenol of 1.5/1. Therefore, some of the active positions have been substituted with alkyl groups. .sup.7 diethanolamine .sup.8 R is the para alkyl group on the .sup.9 ASTM Ring and Ball Softening Point E 28-67
The recipe for the rubber stock used in these evaluations was as follows:
#1RSS - 40 parts -- #1 Ribbed smoked sheets, a grade of natural rubber (described in Vanderbilt's Rubber Handbook, 1968 Edition) which must be dry, clean, free from blemishes, resinous material, sand, dirty packing or other foreign material. Ribbed smoked sheets comprise coagulated rubber sheets properly dried and smoked and cannot contain cuttings, scrap, frothy sheets, weak, heated, or burnt sheets. Air dried or smooth sheets are not permissable.
SBR 1502 - 40 parts -- A standard styrene-butadiene rubber containing 23.5% bound styrene and nominal Mooney Viscosity (ML 1 + 4) at 212° F. of 52. It is non-staining and is prepared using fatty acid-rosin acid type emulsifier and is a standard, cold-polymerized, non-pigmented SBR.
Cis -1,4 - Polybutadiene - 20 parts -- Butadiene homopolymer of high Cis -1,4-content. Budene 501, (Goodyear) is a non-staining, solution polymerized gum with Mooney Viscosity (ML 1 + 4) at 212° F. of 45-55. Cis content is approximately 93%.
N 660 - 45 parts per hundred resin (PHR) - GPF (General Purpose Furnace) -- A carcass grade carbon black with particle diameter about 62 nanometers, DPB absorption .91 cm 3 /g., ASTM iodine No. 36, and bulk density 26 lb/ft 3 .
Circo Light 9 PHR - RPO (Rubber Process Oil) -- Similar to ASTM #3 oil, a napthenic type oil with SUS viscosity 156 at 100° F., specific gravity 0.922 at 60° F., mol. wt. about 330, and anilene point 157° F. Viscosity index intermediate between paraffinic and aromatic oils, manufactured by Sun Oil Co.
Santoflex 13 - 1.9 PHR -- An antiozonant manufactured by Monsanto.
Insoluble Sulfur 60 - 2.75 PHR -- Vulcanizing agent manufactured by Monsanto.
Santocure - 0.9 PHR -- Delayed action accelerator; Monsanto
Santogard PVI - 0.25 PHR -- Pre-vulcanization Inhibitor; Mansanto
Tackifier 3 PHR -- The control in Tables II-IV does not contain any tackifier resin.
Rubber Compounding -- The rubber compound was made in two steps. Step one involved mixing all ingredients except the curatives (sulfur, Santocure and Santogard PVI) in a Banbury mixer for a total of 5-6 minutes at 330° F. The curatives were added in step 2 and the mass was mixed for an additional 2-3 minutes at 220° F.
Tack Test -- The rubber compound was milled to a thickness of 60 mil, and placed on Holland cloth. The exposed side was covered with polyester fabric. The composite was pressed at 200° F. and 75 psi for 2 minutes to remove surface irregularities and to force the polyester reinforcement into the rubber stock. Two 0.75 × 2.0 inch strips were stripped of the Holland cloth, and pressed together. The tack was determined using a Monsanto Tel-tak instrument with a 30 second dwell time and a 16 oz. weight on the sample. Additional samples were held for 72 hours at high humidity, and the tack of these humid-aged samples was determined. The tack values shown in Table II include tack and also the percent tack retention after humid aging (i.e. Example 1 shows 37.5 ± psi at separation with 120% tack retention after humid aging). The separate series I-V are individual testing programs, and the values should be compared with the value for the control (rubber compound without tackifier) in each series.
Table II______________________________________Tack Evaluation.sup.1Example # Control Series______________________________________1 37.5±1.6/120 36 1/634 35.2±1.4/114 " I2 36.9±1.8/120 "3 37.5±1/106 "8 39±2.1/47 39.6±2.2/36 II9 37.6±1.6/48 "1 40.7±2.3/82 39.1±2.5/7310 39±1/89 " III11 36.5±2.1/88 "12 38±1/69 "1 27.4±1.5/105 30.7±1.5/5913 27.1±1.2/103 " IV14 23.2±1.5/112 "1 30±5 1.8/106 28.4±1/2510 27±1.8/53 " V11 28.5±1.1/107 "______________________________________ Humid aging conditions for determining tack retention Series I - 72 hrs. at 80° F. and 70% RH Series II - 72 hrs. at 80° F. and 70 % RH Series III - 72 hrs. at 70° F. and 50% RH Series IV - 72 hrs. at 70° F. and 50% RH Series V - 72 hrs. at 85° F. 90-95% RH
Static Adhesion -- Table III shows the data obtained by testing the ruber stock without tackifier (Control) and with the various tackifying resins, according to ASTM D 2229-73, Adhesion of Vulcanized Rubber to Steel Cord. The steel cord used was National Standard 6-3 wire (brass coated steel). Cure time was T o 1 (90)+ six minutes mold fctor time. Embedment length of wire in the block was 0.75 inches. Table III gives the values, for series I-VI, for both adhesion and coverage (i.e. Example 1, 31±7 pounds required to extract wire, with 10% coverage). Coverage was determined by visual examination by the pulled wire.
Table III______________________________________Static Adhesion Evaluation(ASTM2229)Example # Control Series______________________________________1 31±7/10 93±11/805 26±5/<5 " I6 26±3/<5 "1 59.9±8.6/50 84.6±8.2/804 71.5±8.4/50 "2 50.9±10/50 " II3 50±7.6/30 "1 34±3.4/10 98.9±5.9/707 51.7±7.1/30 "8 118.1±14.8/90 126.5±14.1/90 III9 145.9±15.1/90 "10 138.3±15.1/80 127.8±13.8/7011 103±8.9/80 " IV12 103.2±7.4/80 "13 158.5±16/100 " V14 142.3±7.4/100 "1 121.2±11.4/80 156.6±12.3/9010 174.9±11.5/95 " VI11 183.6±12.4/100 "______________________________________
Table II shows conclusively that the compounds of this invention (Example 8-14) develop the same degree of tack as do conventional, commercially acceptable phenolic tackifiers (Examples 1-4).
Table III shows dramatically the surprising increase in static adhesion which is observed using the compounds of this invention when compared to conventional phenolic tackifiers. Examples 5-7, which are aminomethylene substituted phenolics using other than di 2-alkanolamines or morpholine as the amine do not give the superior results which are obtained by use of morpholine or di-2 hydroxyalkylamines. | Tack is imparted to uncure elastomers by the inclusion of the product of the reaction between an alkylphenol-formaldehyde condensation product having methylol groups with di-2-hydroxyalkylamine or morpholine. In addition to imparting tack to the elastomer, the tackifier of this invention does not interfere with but tends to enhance the development of adhesion of the elastomer to reinforcing fibers. | 2 |
[0001] This application is a divisional of co-pending U.S. application Ser. No. 11/342,258, filed Jan. 27, 2006, which is a continuation of U.S. application Ser. No. 09/943,241, filed Aug. 30, 2001, issued as U.S. Pat. No. 7,082,450, which are incorporated herein by reference.
FIELD
[0002] The invention relates to the processing of digital data. It relates more specifically to a method for implementing an approximation of a discrete cosine transform (DCT) and a quantization, which transform and which quantization are to be applied subsequently to digital data, in particular digital image data, for compression of said digital data. It equally relates to a method for implementing a dequantization and an approximation of an inverse discrete cosine transform (IDCT), wherein for decompression of digital data said quantization is to be applied in sequence with said inverse transform to compressed digital data. Finally, the invention relates to an encoder and to a decoder suited to carry out such a compression and such a decompression respectively.
BACKGROUND
[0003] It is known from the state of the art to use a sequence of DCT and quantization for compressing digital data, for instance in order to enable an efficient transmission of this digital data. In particular a compression of digital image data is commonly achieved by using a DCT followed by a quantization of the DCT coefficients obtained by the DCT.
[0004] In a DCT of one-dimensional digital data, a respective sequence of source values of a predetermined number is transformed into transform coefficients. In video coding, the source values can be for instance pixel values or prediction error values. Each of the resulting transform coefficients represents a certain frequency range present in the source data. DCT of values f( ) into coefficients F( ) is defined as:
[0000]
F
(
i
)
=
2
N
C
(
i
)
∑
x
=
0
N
-
1
f
(
x
)
cos
(
(
2
x
+
1
)
π
2
N
)
,
i
=
0
,
1
,
…
,
N
-
1
C
(
k
)
=
{
1
2
,
k
=
0
1
,
k
≠
0
[0005] In this equation, N is the predetermined number of source values in one sequence of source values.
[0006] For compression, image data is usually provided in blocks of two-dimensional digital data. For such data DCT is defined as:
[0000]
F
(
i
,
j
)
=
2
N
C
(
i
)
C
(
j
)
∑
x
=
0
N
-
1
∑
y
=
0
N
-
1
f
(
x
,
y
)
cos
(
(
2
x
+
1
)
π
2
N
)
cos
(
(
2
y
+
1
)
jπ
2
N
)
,
i
=
j
=
0
,
1
,
…
,
N
-
1
C
(
k
)
=
{
1
2
,
k
=
0
1
,
k
≠
0
[0007] DCT is a separable operation. That means that a two-dimensional DCT can be calculated with two consecutive one-dimensional DCT operations. Using the one-dimensional DCT operation is preferred because the complexity of a one-dimensional DCT is relative to N, while the complexity of a two-dimensional DCT is relative to N 2 . For image data having a size of N*N, the total complexity of all the DCT operations is relative to N 3 or N 2 log(N) for fast DCT. Thus large transforms, which also involve many non-trivial multiplications, are computationally very complex. Furthermore, the additionally required accuracy in bits may increase the word width. For complexity reasons DCT is commonly performed only for small block of values at a time, for example 4×4 or 8×8 values, which can be represented in form of a matrix with values f( ) FIG. 1 illustrates a DCT of such a 4×4 matrix 1 .
[0008] First, each row of the matrix 1 is transformed separately to form a once transformed matrix 2 . In the depicted matrix 1 , a separate transformation of each row is indicated by 2-headed arrows embracing all values of the respective row. Then, each column of the once transformed matrix 2 is transformed separately to form the final transformed matrix 3 comprising the transform coefficients F( ). In the depicted matrix 2 , a separate transformation of each column is indicated by 2-headed arrows embracing all values of the respective column.
[0009] The DCT defined by the above equation can also be written in matrix form. To this end, F(i) is first written in a more suitable form
[0000]
F
(
i
)
=
∑
x
=
0
N
-
1
f
(
x
)
A
(
i
,
x
)
,
i
=
0
,
1
,
…
,
N
-
1
A
(
i
,
x
)
=
2
N
C
(
i
)
cos
(
(
2
x
+
1
)
π
2
N
)
[0010] Matrix A is a matrix of DCT basis functions. A two dimensional DCT can then be calculated with:
[0000] Y=A×A T ,
[0000] where matrix X denotes a source value matrix, and where matrix Y denotes the transform coefficients resulting in the DCT. The index T of a matrix indicates that the transpose of the matrix is meant.
[0011] After DCT, the actual compression is achieved by quantization of DCT coefficients. Quantization is achieved by dividing the transform coefficients with quantization values that depend on a quantization parameter qp:
[0000] Y′ ( i,j )= Y= ( i,j )/ Q ( qp )( i,j ),
[0000] where Q(qp) is a quantization matrix, and where Y′(i,j) constitute quantized coefficients. The simplest form of quantization is uniform quantization where the quantization matrix is populated with one constant, for example:
[0000] Q ( qp )( i,j )= qp.
[0012] The quantized coefficients constitute compressed digital data which has for example, after the encoding and possible further processing steps, a convenient form for transmission of said data.
[0013] When the compressed data is to be presented again after storing and/or transmission, it has first to be decompressed again.
[0014] Decompression is performed by reversing the operations done during compression. Thus, the quantized coefficients Y′(i,j) are inverse quantized in a first step by multiplying the quantized coefficients with values of quantization matrix:
[0000] Y ( i,j )= Y′ ( i,j ) Q ( qp )( i,j )
[0015] Next, the dequantized but still transformed coefficients Y(i,j) are inverse transformed in a second step by an inverse discrete cosine transform (IDCT):
[0000] X=A T YA,
[0000] where matrix Y denotes as in the DCT the transformed coefficients, and where matrix X denotes the regained source value matrix.
[0016] If infinite precision is used for all calculations, X will contain exactly the original pixel values. In practice, however, the coefficients are converted to integer values at least after quantization and inverse transform. As a result, the original pixels can not be exactly reconstructed. The more compression is achieved, the more deviation there is from the original pixels.
[0017] If the above described DCT and IDCT are implemented straight-forward, each conversion requires several multiplications, additions and/or subtractions. These operations, however, require on the one hand a significant amount of processor time, and on the other hand, multiplications are quite expensive operations with respect to circuit area in some architectures. In order to be able to transmit for example high quality motion displays, it is thus desirable to dispose of a conversion process which requires fewer multiplication steps without reducing the quality of the data regained in decompression.
[0018] Since the DCT is also a central operation in many image coding standards, it has been widely used, and a variety of solutions for the stated problem has been described in literature. These solutions generally feature the “butterfly operation” and/or combine some calculations from the operator matrix to the quantization step at the end of the DCT process.
[0019] The U.S. Pat. No. 5,523,847 describes for example a digital image processor for color image compression. In order to reduce the number of non-trivial multiplications in DCT, it is proposed in this document to factor the transform matrix in a way that decreases the number of non-trivial multiplications, non-trivial multiplications being multiplications or divisions by a factor other than a power of two. The trivial multiplications can be realized by bit-shifting, hence the name ‘trivial’. More specifically, the transform matrix is factored into a diagonal factor and a scaled factor such that the diagonal factor can be absorbed into a later quantization step that and the scaled factor can be multiplied by a data vector with a minimum of non-trivial multiplications. In addition, it is proposed that remaining non-trivial multiplications are approximated by multiplications by rational numbers, since the computation can then be achieved only with additions, subtractions and shift operations. This leads to a problem in IDCT, however, since with the approximation, there may not exist an exact inverse transform any more for the transform. Therefore, repeating the DCT-IDCT process may result in severe deterioration in image quality. This may happen, e.g., when the image is transmitted several times over a communications link where DCT compression is utilized.
[0020] Another approach is described in a document by Gisle Bjontegaard: “H.26L Test Model Long Term Number 7 (TML-7) draft0”, ITU Video Coding Experts Group, 13th Meeting, Austin, Tex., USA 2-4 Apr., 2001. This document describes a DCT solution constituting the current test model for a compression method for ITU-T recommendation H.26L.
[0021] According to this document, instead of DCT, an integer transform can be used which has basically the same coding property as a 4×4 DCT. In the integer transform, four transform coefficients are obtained from four source data pixels respectively by four linear equations summing the pixels with predetermined weights. The transform is followed or preceded by a quantization/dequantization process, which performs a normal quantization/dequantization. Moreover, a normalization is required, since it is more efficient to transmit data having a normalized distribution than to transmit random data. Since the transform does not contain a normalization, the quantization/dequantization carries out in addition the normalization which is completed by a final shift after inverse transform. The quantization/dequantization uses 32 different quality parameter (QP) values, which are arranged in a way that there is an increase in the step size of about 12% from one QP to the next. Disadvantage of this approach is that it requires a 32-bit arithmetic and a rather high number of operations.
[0022] Another document proceeds from the cited TML-7 document: “A 16-bit architecture for H.26L, treating DCT transforms and quantization”, Document VCEG-M16, Video Coding Experts Group (VCEG) 13th meeting, Austin, USA, 2-4 Apr., 2001, by Jie Liang, Trac Tran, and Pankaj Topiwala. This VCEG-M16 document mainly addresses a 4×4 transform, and proposes a fast approximation of the 4-point DCT, named the binDCT, for the H.26L standard. This binDCT can be implemented with only addition and right-shift operations. The proposed solution can be implemented to be fully invertible for lossless coding.
[0023] The proposed binDCT is based on the known Chen-Wang plane rotation-based factorization of the DCT matrix. For a 16-bit implementation of the binDCT, a lifting scheme is used to obtain a fast approximation of the DCT. Each employed lifting step is a biorthogonal transform, and its inverse also has a simple lifting structure. This means that to invert a lifting step, it is subtracted out what was added in at the forward transform. Hence, the original signal can still be perfectly reconstructed even if the floating-point multiplication results are rounded to integers in the lifting steps, as long as the same procedure is applied to both the forward and the inverse transform.
[0024] To obtain a fast implementation, the floating-point lifting coefficients are further approximated by rational numbers in the format of k/2m, where k and m are integers, which can be implemented by only shift and addition operations. To further reduce the complexity of the lifting-based fast DCT, a scaled lifting structure is used to represent the plane rotation. The scaling factors can be absorbed in the quantization stage.
[0025] The solution proposed in the VCEG-M16 document only requires 16-bit operations assuming that the source values are 9-bit values and less operations than the solution of the TML-7 document. More specifically, it requires for a 1-D DCT of four data values 10 additions and 5 shifts.
[0026] Further documents relating to image data compression are for instance the following, the contents of which are only addressed briefly:
[0027] U.S. Pat. No. 6,189,021, granted Feb. 13, 2001, proposes to employ a set of scaled weighting coefficients in the intrinsic multiplication stage of a six-stage DCT fast algorithm for one of two one-dimensional DCT operations so that a corresponding stage of the DCT fast algorithm for the other one of the one-dimensional DCT operations can be omitted.
[0028] U.S. Pat. No. 5,129,015, granted Jul. 7, 1992, makes use of a method similar to DCT but employing a simpler arithmetic for compressing still images without multiplication.
[0029] U.S. Pat. No. 5,572,236, granted Nov. 5, 1996, relates to a digital image processor for color image compression which minimizes the number of non-trivial multiplications in the DCT process by rearranging the DCT process such that non-trivial multiplications are combined in a single process step.
[0030] PCT application WO 01/31906, published May 3, 2001, relates to a transform-based image compression framework called local zerotree coding.
SUMMARY
[0031] It is an object of the invention to reduce the operations required for conventional DCT and IDCT while avoiding the necessity of non-trivial multiplications. It is also an object of the invention to provide an alternative to known methods which requires less operations than the regular DCT or IDCT. It is further an object of the invention to guarantee a high quality of the digital data after decompression.
[0032] For compression of digital data, the objects of the invention are reached by a method comprising in a first step simplifying a predetermined transform matrix to require less operations when applied to digital data. In a second step, elements of the simplified transform matrix constituting irrational numbers are approximated by rational numbers. In order to compensate for these measures, a predetermined quantization is extended to include the operations which were removed in the simplification of the predetermined transform matrix. The included operations are further adjusted to compensate for the approximation of elements of the simplified transform matrix by rational numbers. Finally, the simplified transform matrix with the approximated elements and the extended quantization are employed as basis for implementing a sequence of a transform and a quantization which are to be applied to digital data that is to be compressed.
[0033] For decompression of compressed digital data, the objects are reached with a method in which a predetermined inverse transform matrix is processed according to the predetermined transform matrix in the proposed method for compression. In addition, a predetermined dequantization is extended according to the extension of the predetermined quantization in the proposed method for compression. The resulting extended dequantization and the resulting simplified inverse transform matrix with approximated elements can then be used as basis for implementing a sequence of a dequantization and an inverse transform which are to be applied to compressed digital data for achieving a decompression.
[0034] The objects of the invention are finally reached with an encoder comprising a corresponding transformer approximating a DCT and a corresponding quantization means, and with a decoder comprising a corresponding dequantization means and a corresponding transformer approximating an IDCT.
[0035] The invention proceeds from the idea that the number of operations required for a DCT can be reduced significantly, if on the one hand, operations are extracted from the transform matrix and absorbed in the quantization, and if on the other hand, the remaining entries not constituting a rational number are approximated by such a rational number. In order to ensure that decompression can be carried out correctly, however, it is proposed that in addition the approximation is compensated in the operations moved to the quantization.
[0036] It is an advantage of the invention that it enables a fast computation of the transform, since it enables a reduction of the number of required operations, e.g. compared to TML-7 and VCEG-M16, thus saving processor time. Still, the invention achieves a quality very close to the solution of the VCEG-M16 document. Since the invention moreover enables a consideration of the inversion properties of the transform operation by compensating the carried out approximations, a degradation of the quality of the processed data, especially at low bit rates, can be avoided. It is thus a further advantage of the invention that a better inversion accuracy is achieved compared e.g. to U.S. Pat. No. 5,523,847.
[0037] Preferred embodiments of the invention become apparent from the subclaims.
[0038] The proposed step of simplifying the predetermined transform matrix to require less operations when applied to digital data preferably comprises factoring the predetermined transform matrix into two factors, one factor constituting a diagonal matrix and the other factor constituting a simplified transform matrix. The diagonal matrix then comprises the operations removed from the simplified transform matrix.
[0039] Advantageously, the rational numbers by which the remaining entries of the simplified transform matrix are approximated are given by fractions with a denominator of 2 n , wherein n is an integer. Such rational numbers are particularly suited for binary arithmetic, since a multiplication or division by 2 n can be realized by bit-shift operations. Thus all multiplications can be avoided in DCT with the proposed approximation.
[0040] For a given transform matrix, e.g. a 4×4 DCT matrix, and for a selected rational number for approximating remaining entries in the simplified matrix, a single set of equations including only additions, subtractions and shifts can then be determined for each one-dimensional transform that has to be performed for transforming one- or two-dimensional digital data values.
[0041] The adjustment to the approximation in the quantization step preferably ensures that the applied transform has an inverse transform. This can be achieved by ensuring that A T A=I, where matrix A is in this case a matrix for which all extracted operations were re-included in the simplified transform matrix after approximation of the remaining entries and after compensation of the approximation in the extracted operations. This guarantees that an approximation of an IDCT can be performed with good quality.
[0042] For a given transform matrix, e.g. a 4×4 DCT matrix, and for a selected rational number for approximating remaining entries in the simplified matrix, also the required adjustment of specific values in the extracted operations can be calculated in a general way.
[0043] However, in larger transforms like the 8×8 transform, it may additionally be necessary to adjust the approximations of the simplified matrix, since approximating the DCT transform coefficients in an optimized implementation leads to a forward-inverse transform pair that is incomplete, leading to a “spill” of pixel values to non-adjacent, i.e. 2 pixels away, pixels. This results in blurring of the image. By a correct choice of the approximations, the off-diagonal elements of the matrix resulting from forward and inverse transform of a unity matrix are nullified. In very large matrices, it may not be possible to adjust the approximations sufficiently. In such cases, the approximations may be adjusted to produce an optimal result in the least-squares sense. Furthermore, optimization is needed to limit the solutions to a Dirichlet set, i.e., to certain rational numbers.
[0044] For the proposed quantization step, preferably a quantization matrix is determined by multiplying a predetermined sequence of quantization coefficients with a matrix extracted from the transform matrix for simplifying the transform matrix. The extracted matrix comprises the operations extracted from the predetermined transform matrix and is adjusted to compensate for the approximation of remaining entries in the simplified transform matrix by rational numbers.
[0045] The proposed method can be employed equally for one-dimensional as for a two-dimensional transforms. For a two-dimensional transform to be applied to two-dimensional digital data, simplification and approximation is carried out for the predetermined transform matrix and for the transpose of the simplified transform matrix. These two matrices are then employed as basis for implementing the transform. The extended quantization includes in this case operations removed from both of said matrices, which operations are adjusted to compensate for the approximations in both of said matrices.
[0046] The presented preferred embodiments can be employed not only for the method according to the invention for implementing transform and quantization, but in a corresponding manner also for the method for implementing inverse transform and dequantization, for the encoder and for the decoder according to the invention.
[0047] In practice, the transform matrices calculated for transform can usually be used in transposed form for inverse transform without performing any separate calculations, if the operator matrix for the transform is unitary, like a DCT transform matrix. In this case, equally the operations to be included in the extended quantization can be used at the same time for the extension of a predetermined dequantization.
[0048] The invention can be employed for the compression of any kind of digital data for any purpose, e.g. in a mobile communications system like GSM (Global System for Mobile communication) or UMTS (Universal Mobile Telecommunication System).
[0049] The invention can be implemented for example as a part of an MPEG codec.
[0050] Other objects and features of the present invention will become apparent from the following detailed description considered in conjunction with the accompanying drawings. It is to be understood, however, that the drawings are designed solely for purposes of illustration and not as a definition of the limits of the invention, for which reference should be made to the appended claims instead.
BRIEF DESCRIPTION OF THE FIGURES
[0051] In the following, the invention is explained in more detail with reference to drawings, of which
[0052] FIG. 1 illustrates a DCT applied to a matrix of 4×4 values; and
[0053] FIG. 2 schematically shows a block diagram of an encoder and of a decoder employed for compressing and decompressing digital data according to an embodiment of the invention.
DETAILED DESCRIPTION
[0054] FIG. 1 has already been described above.
[0055] The block diagram of FIG. 2 includes components of an exemplary system in which the invention can be realized. On the left-hand side of FIG. 2 , an encoder 4 is depicted. The encoder 4 is part of a first unit, e.g. a piece of user equipment of a mobile communications system, capable of providing and transmitting video data. Connected between its input and its output, the encoder 4 comprises a DCT transformer 41 , a quantization means 42 and additional means 43 . On the right-hand side of FIG. 2 , a decoder 5 is depicted. The decoder 5 is part of a second unit, e.g. equally a piece of user equipment of a mobile communications system, capable of receiving and displaying video data. Connected between its input and its output, the decoder 5 comprises a means 53 , a dequantization means 53 and an IDCT transformer 51 .
[0056] In case video data is to be transmitted from the first unit to the second unit, e.g. via a communications network, the video data is provided to the encoder 4 of the first unit as digital data. In the encoder 4 , the digital data is first transformed by the DCT transformer 41 , and then quantized by the quantization means 42 . After quantization, the data is further processed by the additional means 43 . This processing includes encoding of the quantized data for transmission, possibly preceded by a further compression, and is not dealt with in this document, since it is not relevant to the invention.
[0057] The processed data is then transmitted from the first unit comprising the encoder 4 to the second unit comprising the decoder 5 . The second unit receives the data and forwards it to the decoder 5 . In the decoder 5 , in a first step some processing is carried out in the means 53 , which processing corresponds in an inverse way to the processing in block 43 of the encoder 4 . Thus, the processing, which is not dealt with in this document, may include decoding, followed possibly by a first step of decompression. The processed data is then dequantized by the dequantization means 52 and moreover subjected to an IDCT by the IDCT transformer 51 . The regained video signals provided by the IDCT 51 are output by the decoder 5 for display by the second unit to a user.
[0058] An embodiment of an implementation according to the invention of the DCT transformer 41 and of the quantization means 42 of the encoder 4 of FIG. 2 will now be derived. For this implementation, which proceeds from the DCT and the quantization as described in the background of the invention, it is assumed that compression of input digital image data is to be carried out for blocks of digital data comprising 4×4 values. An embodiment of an implementation according to the invention of a corresponding decompression by the dequantization means 52 and the IDCT transformer 51 of the decoder 5 of FIG. 2 will be indicated as well.
[0059] It is to be noted that in the presented equations, the same denomination may be employed in different equations for different matrices. The kind of the respective matrices will be indicated for each equation at least if a corresponding denomination was used before for another kind of matrix.
[0060] In accordance with the above mentioned equation for DCT, Y=A×A T , the 4×4 forward DCT transform can be calculated as follows:
[0000]
Y
=
AXA
T
=
[
a
a
a
a
b
c
-
c
-
b
a
-
a
-
a
a
c
-
b
b
-
c
]
·
[
x
11
x
12
x
13
x
14
x
21
x
22
x
23
x
24
x
31
x
32
x
33
x
34
x
41
x
42
x
43
x
44
]
·
[
a
b
a
c
a
c
-
a
-
b
a
-
c
-
a
b
a
-
b
a
-
c
]
,
[0000] where Y is the desired transformed matrix, where X is a matrix containing the 4×4 source values x ij (i,j=1-4), and where A is the 4×4 DCT transform matrix. The values a, b and c of matrix A can be obtained easily from the above definition for A(i,x):
[0000] a= ½
[0000] b= √{square root over (½)} ·cos(π/8)
[0000] c= √{square root over (½)} ·cos(3π/8)
[0061] In the equation for the forward DCT, matrix A can be factorized, resulting in a diagonal matrix B and a simplified transform matrix C. A corresponding factorization can be carried out for the transposed form of A, A T . If d is denoted in addition as d=c/b, the forward DCT can be written as
[0000]
Y
=
BCXC
T
B
=
[
a
0
0
0
0
b
0
0
0
0
a
0
0
0
0
b
]
·
[
1
1
1
1
1
d
-
d
-
1
1
-
1
-
1
1
d
-
1
1
-
d
]
·
[
x
11
x
12
x
13
x
14
x
21
x
22
x
22
x
24
x
31
x
32
x
33
x
34
x
41
x
42
x
43
x
44
]
·
[
1
1
1
d
1
d
-
1
-
1
1
-
d
-
1
1
1
-
1
1
-
d
]
·
[
a
0
0
0
0
b
0
0
0
0
a
0
0
0
0
b
]
[0062] Since B is a diagonal matrix, the above equation can be written as
[0000]
Y
=
D
⊗
(
CXC
T
)
⊗
D
T
=
[
a
a
a
a
b
b
b
b
a
a
a
a
b
b
b
b
]
⊗
(
[
1
1
1
1
1
d
-
d
-
1
1
-
1
-
1
1
d
-
1
1
-
d
]
·
[
x
11
x
12
x
13
x
14
x
21
x
22
x
22
x
24
x
31
x
32
x
33
x
34
x
41
x
42
x
43
x
44
]
·
[
1
1
1
d
1
d
-
1
-
1
1
-
d
-
1
1
1
-
1
1
-
d
]
)
⊗
[
a
b
a
b
a
b
a
b
a
b
a
b
a
b
a
b
]
[0000] where is used to indicate that the respective two matrices are multiplied entry-wise instead of a full matrix multiplication.
[0063] After combining D and its transposed form D T into E, the final DCT is:
[0000]
Y
=
(
CXC
T
)
⊗
E
=
(
[
1
1
1
1
1
d
-
d
-
1
1
-
1
-
1
1
d
-
1
1
-
d
]
·
[
x
11
x
12
x
13
x
14
x
21
x
22
x
22
x
24
x
31
x
32
x
33
x
34
x
41
x
42
x
43
x
44
]
·
[
1
1
1
d
1
d
-
1
-
1
1
-
d
-
1
1
1
-
1
1
-
d
]
)
⊗
[
a
2
ab
a
2
ab
ab
b
2
ab
b
2
a
2
ab
a
2
ab
ab
b
2
ab
b
2
]
=
Y
C
⊗
E
[0064] In a next step, the coefficient d is converted into a fixed-point format which can be represented by a rational fraction with a denominator of 2 n . The value of d when considering eight decimal places is 0.41421356. Two of the possible fixed-point approximations for d are ⅜=0.375 and 7/16=0.4375, both of which can be implemented with the same number of add and shift operations. More accurate approximations such as 13/32, 27/64 and 53/128 require more additions and shifts but do not improve the achieved compression significantly in practice. Thus, 7/16, which is closer to d than ⅜, is selected as fixed-point format for d.
[0065] After converting coefficient d to a fixed-point representation, b has to be adjusted in a way that the transform has an inverse transform. The condition for an inverse transform to exist is given by:
[0000] A T A=I.
[0066] When solving the above equation for a matrix A which was reassembled from factors B and C after the approximation of d, the condition for an adjusted b is found to be:
[0000]
b
=
0.5
1
+
d
2
.
[0067] Matrix E is thus adjusted by substituting this new value for the old value of coefficient b.
[0068] Now, a simplified DCT can be implemented in the DCT transformer 41 of encoder 4 from which matrix E was extracted. That is, the implementation is based on the equation Y C =C×C T , wherein matrix C comprises approximated coefficients d, resulting in modified DCT coefficients Y C . Matrix E will combined with the subsequent quantization step, as will be explained below.
[0069] The actual implementation of the simplified DCT may depend on a specific transformer architecture, in which it may be most important to have few total operations or to have no multiplications at all.
[0070] Two different sets of equations that can be employed in an implementation of the simplified DCT transformer will now be proposed. The equations are suited to perform a 4-point one-dimensional simplified DCT which is based on simplified DCT transform matrix C as derived above. In matrix C, coefficient d is chosen to be d= 7/16. In both sets of equations, X[i], i=0-3 constitutes a sequence of 4 values that are to be transformed and Y[i], i=0-3 a sequence of 4 transformed values, while e and f are auxiliary variables.
[0071] The first proposed set of equations is:
[0000] e=X[ 0 ]+X[ 3]
[0000] f=X[ 1 ]+X[ 2]
[0000] Y[ 0 ]=e+f
[0000] Y[ 2 ]=e−f
[0000] e=X[ 0 ]−X[ 3]
[0000] f=X[ 1 ]−X[ 2]
[0000] Y[ 1 ]=e+ 7 *f/ 16
[0000] Y[ 3]=7* e/ 16− f
[0072] The two divisions in this set of equations are actually bit shifts. This set of equation thus requires 8 additions 2 multiplications and 2 shifts for a total of 12 operations.
[0073] The second proposed set of equations is:
[0000] e=X[ 0 ]+X[ 3]
[0000] f=X[ 1 ]+X[ 2]
[0000] Y[ 0 ]=e+f
[0000] Y[ 2 ]=e−f
[0000] e=X[ 0 ]−X[ 3]
[0000] f=X[ 1] −X[ 2]
[0000] Y[ 1]= e +( f−f/ 8)/2
[0000] Y[ 3]=( e−e/ 8)/2 −f
[0074] The second set of equations uses only additions and shifts, and produces identical results to the first set. Again, divisions are actually bit shifts. This version requires 10 additions and 4 shifts for total of 14 operations. The number of operations is larger than in the first version, but the resulting complexity is still lower if multiplication is an expensive operation. Moreover, the results of a multiplication require a larger dynamic range.
[0075] Either set of equations can be used for transforming two-dimensional data by applying it to the respective set of values that is to be transformed.
[0076] The simplified transform is followed by an adapted quantization step. The implementation of the quantization depends on the used DCT. In the above mentioned TML-7 document, a uniform quantization is used. In fast DCT, a non-uniform quantization matrix must be used, since some of the DCT multiplications are combined with quantization multiplications. The above mentioned binDCT of document VCEG-M16 moreover uses divisions for quantization and requires only 16-bit operations. A division, however, is generally a rather slow operation. Therefore, in the presented embodiment a uniform quantization using only multiplications is implemented in quantization means 42 .
[0077] As already mentioned above, quantization can be performed using division so that
[0000] Y ′( i,j )= Y ( i,j )/ Q ( qp )( i,j ).
[0078] Since division is a costly operation, multiplication can be used instead. For this purpose quantization matrix R is calculated as
[0000] R ( qp )( i,j )=1.0 /Q ( qp )( i,j ),
[0000] after which quantization can be performed with multiplication:
[0000] Y′ ( i,j )= Y ( i,j ) R ( qp )( i,j ).
[0079] In the quantization proposed in document TML-7, the quantization coefficients are approximately as shown below. Other coefficients could be used as well.
[0000] a(qp)=
2.5000, 2.8061, 3.1498, 3.5354, 3.9684, 4.4543, 4.9998, 5.6120, 6.2992, 7.0706, 7.9364, 8.9082, 9.9990, 11.2234, 12.5978, 14.1404, 15.8720, 17.8155, 19.9971, 22.4458, 25.1944, 28.2795, 31.7424, 35.6293, 39.9922, 44.8894, 50.3863, 56.5562, 63.4817, 71.2552, 79.9806, 89.7745.
[0080] In order to be able to absorb the matrix E extracted from the DCT in the quantization, a quantization matrix R for quantization parameter qp is calculated as
[0000] R ( qp )( i,j )=· E ( i,j )/ a ( qp )
[0081] The final quantized coefficients Y′(i,j) could now be determined from the transform coefficients Y C (i,j) resulting in the simplified DCT by
[0000] Y′ ( i,j )= Y C ( i,j )· R ( qp )( i,j )± f
[0000] where f is ⅓ for intra blocks and ⅙ for inter blocks and has the same sign as Y C (i,j) in accordance with the TML-7 documentation. An intra block is a macroblock which is encoded based only on values within the current image, while an inter block is a macroblock which is encoded based in addition on values within other images. Each macroblock is composed of several subblocks, e.g. the blocks of 4×4 values of the presented example, which are DCT transformed and quantized separately.
[0082] First, however, the quantization is changed to use only fixed-point values. To this end, the values of R and f are converted prior to quantization to fixed point values by multiplying them by 2 n and by rounding the results to integer values. n is the number of fractional bits used for the fixed-point values. By choosing n=17, the coefficients of R will fit in 16-bit, and thus only 16-bit multiplications are required in quantization. More specifically, 16-bit multiplications are required that produce 32-bit results.
[0083] The fixed-point quantization is then implemented in quantization means 42 of encoder 4 based on the equation:
[0000] Y′ ( i,j )=( Y C ( i,j )· R ( qp )( i,j )± f )/2″,
[0000] where R and f comprise only fixed-point values. The values of Y′(i,j) are output by the quantization means 42 as the desired compressed digital image data.
[0084] For decompression of the compressed digital image data in the decoder 5 of FIG. 2 , the dequantization means 52 and the IDCT transformer 53 are implemented in a corresponding way as the quantization means 42 and the DCT transformer 41 of encoder 4 . The basic IDCT is calculated from the basic DCT as:
[0000] X=A T YA,
[0000] where matrix X contains the desired, regained source values, where matrix A is the original DCT transform matrix, and where matrix Y contains dequantized values obtained by a decompression as described in the background of the invention.
[0085] Proceeding from this equation, the inverse transform can be formulated correspondingly to the forward transform using an extracted matrix E:
[0000] X=C T ( Y E ) C.
[0000] where matrices C and C T correspond to the matrices C and C T used for the reduced DCT in block 41 of the encoder 4 .
[0086] Matrix E of this equation can be absorbed in the dequatization step preceding the IDCT.
[0087] This can be realized similarly to absorbing matrix E in quantization. Dequantization coefficients are inverse values of the quantization coefficients.
[0088] A dequantization matrix Q for a quantization parameter qp including matrix E can be calculated as:
[0000] Q ( qp )( i,j )= E ( i,j )· a ( qp )
[0089] The compressed coefficients Y′(i,j) can therefore be dequantized to dequantized coefficients X′(i,j) according to the equation:
[0000] X ′( i,j )= Y ′( i,j )· Q ( qp )( i,j ).
[0090] In this equation, X′(i,j) corresponds to the term Y E in the above equation for inverse transform X=C T (Y E)C.
[0091] When fixed-point numbers are used, values of Q are converted to fixed-point values prior to dequantization by multiplying them by 2″ and rounding results to integer values. By choosing n=5 for dequantization, all calculations in dequantization can be done using only 16-bit operations. Fixed-point dequantization is then implemented in dequantization means 52 of decoder 5 based on the equation:
[0000] X ′( i,j )= Y ( i,j )· Q ( qp )( i,j ),
[0000] in which Q contains only fixed-point numbers. After dequantization the values of X′(i,j) should be normalized by 2 n , but normalization is postponed to be done after final IDCT in order to achieve a better accuracy.
[0092] The simplified inverse transform can then be implemented in the IDCT transformer 51 of decoder 5 according to the equation:
[0000] X=C T X′C
[0000] after which fixed-point values of X are converted to integer values based on the equation:
[0000] X ( i,j )=( X ( i,j )+2 n-1 )/2 n ,
[0000] where the division by 2 n is realized with a simple arithmetic bit-shift.
[0093] The actual implementation of the IDCT transformer 51 can comprise a set of equations including only additions, subtractions and shifts corresponding to those presented for the DCT transformer 41 .
[0094] According to another embodiment of the invention, an 8×8 DCT and IDCT can be implemented as presented in the following. In accordance with the equation for DCT, Y=A×A T , the 8×8 forward DCT transform can be calculated as follows:
[0000]
Y
=
AXA
T
=
[
a
a
a
a
a
a
a
a
b
c
d
e
-
e
-
d
-
c
-
b
f
g
-
g
-
f
-
f
-
g
g
f
c
-
e
-
b
-
d
d
b
e
-
c
a
-
a
-
a
a
a
-
a
-
a
a
d
-
b
e
c
-
c
-
e
b
-
d
g
-
f
f
-
g
-
g
f
-
f
g
e
-
d
c
-
b
b
-
c
d
-
e
]
·
X
·
A
T
,
[0000] where Y is the desired transformed matrix, where X is a matrix containing the 8×8 source values x ij (i,j=1-8), as above in the 4×4 embodiment, where A is the 8×8 DCT transform matrix, written open on the right-hand side of the equation, and where A T is the transpose of A. The values a, b, c, d, e, f and g of matrix A can be obtained easily from the above definition for A(i,x):
[0000] a= 1/(2√{square root over (2)})
[0000] b= ½·cos(π/16)
[0000] c= ½·cos(3π/16)
[0000] d= ½·cos(5π/16)
[0000] e= ½·cos(7π/16)
[0000] f= ½·cos(π/8)
[0000] g= ½·cos(3π/8)
[0095] In the equation for the forward DCT, matrix A can be factorized, resulting in a diagonal matrix B and a simplified transform matrix C. A corresponding factorization can be carried out for the transposed form of A, A T . If we use the notation x y =x/y, the forward DCT can be written as
[0000]
Y
=
BCXC
T
B
=
[
a
0
0
0
0
0
0
0
0
b
0
0
0
0
0
0
0
0
f
0
0
0
0
0
0
0
0
b
0
0
0
0
0
0
0
0
a
0
0
0
0
0
0
0
0
b
0
0
0
0
0
0
0
0
f
0
0
0
0
0
0
0
0
b
]
·
[
1
1
1
1
1
1
1
1
1
c
b
d
b
e
b
-
e
b
-
d
b
-
c
b
-
1
1
g
f
-
g
f
-
1
-
1
-
g
f
g
f
1
c
b
-
e
b
-
1
-
d
b
d
b
1
e
b
-
c
b
1
-
1
-
1
1
1
-
1
-
1
1
d
b
-
1
e
b
c
b
-
c
b
-
e
b
1
-
d
b
g
f
-
1
1
-
g
f
-
g
f
1
-
1
g
f
e
b
-
d
b
c
b
-
1
1
-
c
b
d
b
-
e
b
]
·
X
·
C
T
·
B
[0096] Since B is a diagonal matrix, the above equation can, as in the 4×4 case, be written as
[0000]
Y
=
D
⊗
(
CXC
T
)
⊗
D
T
=
[
a
a
a
a
a
a
a
a
b
b
b
b
b
b
b
b
f
f
f
f
f
f
f
f
b
b
b
b
b
b
b
b
a
a
a
a
a
a
a
a
b
b
b
b
b
b
b
b
f
f
f
f
f
f
f
f
b
b
b
b
b
b
b
b
]
⊗
(
CXC
T
)
⊗
[
a
b
f
b
a
b
f
b
a
b
f
b
a
b
f
b
a
b
f
b
a
b
f
b
a
b
f
b
a
b
f
b
a
b
f
b
a
b
f
b
a
b
f
b
a
b
f
b
a
b
f
b
a
b
f
b
a
b
f
b
a
b
f
b
]
[0000] where is used to indicate that the respective two matrices are multiplied entry-wise instead of a full matrix multiplication. After combining D and its transposed form D T into E, the final DCT is
[0000]
Y
=
(
CXC
T
)
⊗
E
=
(
[
1
1
1
1
1
1
1
1
1
c
b
d
b
e
b
-
e
b
-
d
b
-
c
b
-
1
1
g
f
-
g
f
-
1
-
1
-
g
f
g
f
1
c
b
-
e
b
-
1
-
d
b
d
b
1
e
b
-
c
b
1
-
1
-
1
1
1
-
1
-
1
1
d
b
-
1
e
b
c
b
-
c
b
-
e
b
1
-
d
b
g
f
-
1
1
-
g
f
-
g
f
1
-
1
g
f
e
b
-
d
b
c
b
-
1
1
-
c
b
d
b
-
e
b
]
·
X
·
C
T
)
⊗
[
a
2
ab
af
ab
a
2
ab
af
ab
ab
b
2
bf
b
2
ab
b
2
bf
b
2
af
bf
f
2
bf
af
bf
f
2
bf
ab
b
2
bf
b
2
ab
b
2
bf
b
2
a
2
ab
af
ab
a
2
ab
af
ab
ab
b
2
bf
b
2
ab
b
2
bf
b
2
af
bf
f
2
bf
af
bf
f
2
bf
ab
b
2
bf
b
2
ab
b
2
bf
b
2
]
=
Y
C
⊗
E
[0097] In a next step, the coefficients c b , d b , e b and g f are converted into a fixed-point format which can be represented by a rational fraction with a denominator of 2 n . Close approximations are c b =⅞, d b = 9/16, e b = 3/16 and g f = 7/16.
[0098] After converting coefficients c b , d b , e b and g f to a fixed-point representation, b and f have to be adjusted in a way that the transform has an inverse transform. The condition for an inverse transform to exist is again given by:
[0000] A T A=I.
[0099] When solving the above equation for a matrix A which was reassembled from factors B and C after the approximation of c b , d b , e b and g f , the condition for adjusted b and f are found to be:
[0000]
b
=
1
2
1
1
+
c
b
2
+
d
b
2
+
e
b
2
f
=
1
2
1
1
+
g
f
2
.
,
[0100] Matrix E is thus adjusted by substituting these new value for the old value of coefficients b and f.
[0101] However, to fulfill the condition A T A=I, the values for c b , d b and e b have to be chosen differently, since otherwise the product A T A features non-zero off-diagonal elements. The necessary condition for the 8×8 case is
[0000] d b −c b +e b ( d b +c b )=0,
[0000] which can be fulfilled by choosing c b = 15/16, d b = 9/16 and e b =¼.
[0102] Now, a simplified DCT can again be implemented in the DCT transformer 41 of encoder 4 from which matrix E was extracted. That is, the implementation is based on the equation Y C =C×C T , wherein matrix C comprises approximated coefficients c b , d b , e b and g f , resulting in modified DCT coefficients Y C . Matrix E will be combined with the subsequent quantization step similarly as explained above for the 4×4 DCT.
[0103] According to a third embodiment of the invention, the approximations are adjusted for the condition A T A=I by optimizing the selection of fractional numbers in the transform. The fractional numbers are selected so that the off-diagonal elements of the matrix A T A are as close to zero as possible in the implementation sense. The solution of the optimization is limited to a Dirichlet set, i.e., to certain rational numbers.
[0104] According to a fourth embodiment of the invention approximations of a fast-DCT algorithm are adjusted for the condition A T A=I by optimizing the selection of fractional numbers in the transform.
[0105] In the whole, it becomes apparent from the described embodiments of the invention that efficient alternative implementations for compressing digital data are presented. The implementation can be realized to be either more accurate than known implementations or faster or both.
[0106] Thus, while there have been described and pointed out fundamental novel features of the invention as applied to a preferred embodiment thereof, it will be understood that various omissions and substitutions and changes in the form and details of the devices and methods described may be made by those skilled in the art without departing from the spirit of the invention. For example, it is expressly intended that all combinations of those elements and/or method steps which perform substantially the same function in substantially the same way to achieve the same results are within the scope of the invention. Moreover, it should be recognized that structures and/or elements and/or method steps shown and/or described in connection with any disclosed form or embodiment of the invention may be incorporated in any other disclosed or described or suggested form or embodiment as a general matter of design choice. It is the intention, therefore, to be limited only as indicated by the scope of the claims appended hereto. | An approximation of a DCT and a quantization are to be applied subsequently to digital data for compression of this digital data. In order to improve the transform, a predetermined transform matrix is simplified to require less operations when applied to digital data. In addition, elements of the simplified transform matrix constituting irrational numbers are approximated by rational numbers. These measures are compensated by extending a predetermined quantization to include the operations which were removed in the simplification of the predetermined transform matrix. The included operations are further adjusted to compensate for the approximation of elements of the simplified transform matrix by rational numbers. If the simplified transform matrix and the extended quantization are used as basis for implementation, a fast transform with a good resulting quality can be achieved. An approximation of an IDCT employed in decompression of compressed digital data can be simplified correspondingly. | 7 |
FIELD OF THE INVENTION
The present invention relates to computer environments, more specifically to data backup.
BACKGROUND OF THE INVENTION
It is a common practice to back up data in a computer environment. When the data is backed up to a backup medium, such as a tape drive or a hard drive, additional information, herein referred to as the index, can also be delivered from the computer system which is backing up its data. The index provides information about the data that is being backed up, such as how the backup data is organized. The index is often received in a random order and the received index typically needs to be reorganized. For a large number of indexes, the organization of the index at the end of the backup, can take a very long time and consume high system resources. It would be desirable to be able to organize the index in a way that avoids the extremely long time periods typically required to rebuild the index.
BRIEF DESCRIPTION OF THE DRAWINGS
Various embodiments of the invention are disclosed in the following detailed description and the accompanying drawings.
FIG. 1 is a block diagram of a system suitable for executing the invention.
FIGS. 2A-2B are flow diagrams of a method according to some embodiments for processing an index.
FIG. 3 is a flow diagram of a method for processing an index according to some embodiments.
FIG. 4 is an example of a index tree as discussed in conjunction to FIG. 3 with index entries identified by inode numbers according to some embodiments.
FIG. 5 is a flow diagram of a method for index processing according to some embodiments.
DETAILED DESCRIPTION
The invention can be implemented in numerous ways, including as a process, an apparatus, a system, a composition of matter, a computer readable medium such as a computer readable storage medium or a computer network. In this specification, these implementations, or any other form that the invention may take, may be referred to as techniques. In general, the order of the steps of disclosed processes may be altered within the scope of the invention.
A detailed description of one or more embodiments of the invention is provided below along with accompanying figures that illustrate the principles of the invention. The invention is described in connection with such embodiments, but the invention is not limited to any embodiment. The scope of the invention is limited only by the claims and the invention encompasses numerous alternatives, modifications and equivalents. Numerous specific details are set forth in the following description in order to provide a thorough understanding of the invention. These details are provided for the purpose of example and the invention may be practiced according to the claims without some or all of these specific details. For the purpose of clarity, technical material that is known in the technical fields related to the invention has not been described in detail so that the invention is not unnecessarily obscured.
FIG. 1 is a block diagram of a system suitable for executing the invention. In this example, a data server 100 is shown to send data to a backup medium 102 . The data server 100 also sends the index to backup server 104 .
FIG. 2 is a flow diagram of a method according to some embodiments for processing an index. In this example, an index is received in pieces. For example, an index for a particular piece of data may have a DIR component and a NODE component, wherein the DIR includes an inode number, parent inode number, and name of the index. In this embodiment, the inode number is a unique number identifying the index. The NODE component of the index also includes the inode number that matches the DIR inode number, as well as index attributes, such as stat info. Examples of stat info include information about the index such as size, type, permissions, creation and modification date.
In this example, an index component is received ( 200 ). An index component as used herein is a portion of an index, such as a DIR component or a NODE component. It is then determined whether the inode number of the index component is already stored ( 202 ). In one embodiment, the inode number is stored in an on-disk balancing tree structure such as a B+ tree. The B+ tree structure can be used in conjunction with a search library, such as WISS from Legato, Inc., a division of EMC. In some embodiments, an inode number can be a unique number identifying an index and all of the index components of that index are associated with that number.
If the inode number of this particular index is not found to be stored, then the received index component is stored as a new entry ( 208 ). For example, if a NODE component is received and inode number of this particular index is not found to be stored in the balancing tree on disk, then this received component is stored in the balancing tree as a new entry.
If the inode number of this particular index is found to be stored, then it is determined whether the received index component is a DIR ( 204 ). If it is not a DIR, then it is assumed to be a NODE component and it is written in the same entry as the matching stored inode numbers for all matching inode numbers ( 210 ). If the received index component is a DIR ( 204 ), then it is determined whether the matching stored index entry includes a NODE ( 206 ). If not, then the received DIR is stored as a new entry ( 212 ).
If the matching stored index entry includes a NODE ( 206 ), then it is determined whether one of the matching stored index entries is a DIR ( 220 ). If no DIR components with the matching inode number are already stored but there is a NODE entry, then the matching NODE entry is updated with this received DIR component ( 224 ). If, however, one of the matching stored index entries is a DIR ( 220 ), then the NODE attribute is copied from one of the matching entries and stored with the receiving DIR component in a new entry ( 222 ).
FIG. 3 is a flow diagram of a method for processing an index according to some embodiments. In this example, the pieces of the indexes have been restructured, stored in the balancing tree as index entries, and the index tree is being reconstructed. FIG. 3 is best understood when discussed in conjunction with FIG. 4 .
FIG. 4 is an example of an index tree as discussed in conjunction with FIG. 3 , with indexes identified by inode numbers according to some embodiments. In this example, the tree is shown to include an index structure with the top index having the inode number 2 . Indexes with inode numbers 3 and 4 are shown to be the children of the inode number 2 ; and inode numbers 5 , 6 , 7 , and 8 being the children of inode numbers 3 and 4 . Inode number 2 is herein referred to as the parent of inode number 3 and inode number 4 ; and inode number 3 is referred to as the parent of inode number 5 and inode number 6 . In this example, inode number 2 can be a directory which includes a directory with inode number 3 and another directory with inode number 4 . Inode number 3 is a directory with a file having the inode number 5 and another file having the inode number 6 .
In the example shown in FIG. 3 , the topmost inode number is found from the stored inode numbers ( 300 ). For example, it can be predetermined that the topmost inode number in the tree is inode number 2 . Accordingly, a search can be performed in the balancing tree, such as a B+tree, to find inode number 2 .
Index entries whose parents are the topmost inode number are then found ( 302 ). For example, in the example shown in FIG. 4 , the indexes whose parents are the topmost inode number is inode number 3 and inode number 4 . Accordingly, a search can be performed in the balancing tree based on parent information to find the index entries with parent equaling inode number 2 . In some embodiments, the parent inode number is stored in the DIR component of the index.
These index entries are identified as the next level of the index tree ( 304 ). It is then determined whether there are entries with these inode numbers as parents ( 306 ). If there are no index entries with these inode numbers as parents, then the restructuring is complete. If, however, there are entries with these inode numbers as parents, then the newly discovered index entries are identified as the next level of the index tree ( 304 ).
FIG. 5 is a flow diagram of a method for index processing according to some embodiments. In this example, the index is delivered from the data server to the backup server in a single piece rather than receiving multiple pieces of an index. Here, the inode number is not received, rather the path of the index is received. For example, index d can be received with the path of a/b/c/d, where c is the parent of d, b is the parent of c, and a is the parent of b. In addition, another index d, along with its path, can be received, where index d is not the same as index d. A file with the same name can occur under different directories for example a/c/b/d, where these files do not have the same path. Accordingly, a search by name, such as d, is not in helpful in this example. In some embodiments, a pseudo inode number is generated for the entries in the path. In some embodiments, this inode number is unique. A directory tree can be generated in memory which includes the index name, its assigned inode number, and its parent's assigned inode number such that a quick search can be performed by searching for either the inode number or the parent inode number.
In the example shown in FIG. 5 , an index is received with a path for the index, such as a/b/c/d ( 500 ). It is determined whether a path entry is retrieved from the path ( 502 ). If a path entry is not retrieved from the path, then the process is complete. If a path entry, such as “b”, is retrieved from the path, then the parent inode number is retrieved from a directory tree ( 504 ). The directory tree includes a list of directories. In some embodiments, the directory tree is stored in memory while the index tree is stored on disk. It is then determined whether the path entry is in the directory tree ( 506 ). If the path entry is already in the directory tree, then the next entry is retrieved from the received path ( 502 ). In some embodiments, the path entries are retrieved from left to right—from parent to child—such as a, then b, then c, then d in the example of a path a/b/c/d.
If the path entry is not in the directory tree ( 506 ), then a unique inode number is assigned to this path entry ( 508 ) in this example. It is determined whether the path entry is a directory ( 510 ). In some embodiments, files are not saved in the directory tree while directories are saved. Directories have at least one child while files do not. If the path entry is a directory, then it is added to the directory tree ( 512 ). In some embodiments, the directory name, its assigned inode number and its parents assigned inode number are stored in the directory tree. For example, if the path a/b/c/d has been received for index “d”, and “c” has been assigned the inode number 4 and “d” is assigned inode number 5 , then “d”'s parent inode number is 4 . Whether the path entry is added to the directory tree ( 512 ) or the path entry is a directory ( 510 ), the index is stored in the balance tree on disk ( 514 ). The next path entry is then retrieved ( 502 ) if one is available.
Thereafter, the index tree can be rebuilt in some embodiments according to a method similar to that exemplified in FIG. 3 . In this embodiment, the directory tree stored in memory is searched rather than the balancing tree to find the inode numbers and parent inode numbers.
Although the foregoing embodiments have been described in some detail for purposes of clarity of understanding, the invention is not limited to the details provided. There are many alternative ways of implementing the invention. The disclosed embodiments are illustrative and not restrictive. | According to some embodiments, a technique of processing an index comprises receiving a portion of an index, wherein the index is associated with an identifier; determining whether the identifier is stored; and storing the received portion of the index in substantially the same entry as the stored identifier, if it is determined that the identifier is stored. | 8 |
[0001] This application is based on and claims the benefit of priority from prior Argentine Patent Application No. 2013 010713, filed Mar. 5, 2013, the entire contents of which are incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention is related to the field of means or dispositions employed for the temporary storage and treatment of hydrocarbons, more particularly, it refers to a manifold battery that, unlike traditional batteries, reduces the impact on the environment, the consequential accidents, dangers and risks of the flammable, toxic and damaging substances concentration, as well as the operative times and connected costs.
[0003] Even when the present description refers more particularly to the technical and commercial advantages of its implementation as a manifold battery for hydrocarbon fields, it is clear that its use accommodates the pertinent environmental safety rules and cooperates with awareness for the environment.
BACKGROUND
[0004] In order to better understand the purpose and scope of the present invention, it is convenient to describe the current state of the art regarding the traditional manifold tanks or batteries used and the drawbacks that occur.
[0005] Manifold batteries are well known in the field of the art and it is well known that they receive the oil extracted from the wells, to treat the same in a first stage prior to its refining process. A battery is generally used in small plants constituted by a collector or “manifold”, such as it is known in the art, provided in the battery entrance to be connected to the plurality of wells available in the place, and to receive the oil which is simultaneously extracted from them. In turn, it is known that the oil comes accompanied by gas and water, among other components, for which a gas separator, a pair of heaters, a plurality of general production tanks (160 m3) and control tanks (40 m3), some pumps, flowmeters, liquid separators, etc. are provided. Thus, the oil, the water and the natural gas coming from the wells flow are separated in the mentioned tanks and separated by diverse methods, subsequently being prepared for the following treatments or purposes.
[0006] In addition, the storage tanks are designed to store and handle great oil and gas volumes, being generally of big dimensions. The storage constitutes a valuable element in the exploitation of hydrocarbon services since it acts as a core zone between production and/or transportation to absorb the consumption variations. Known tanks comprise a cylindrical form with a flat bottom, vaulted top structure, being floating some times, so as to avoid flammable gas accumulation within them. The tanks may be or not be provided with a heating system.
[0007] On the other hand, in case an extremely dangerous defect or drawback in the mentioned tanks occurs, there will be a containment pool surrounding each of them, in order for a rapid evacuation so as not to damage and impact the environment.
[0008] However, the batteries' infrastructure demands high economic investments. This occurs since the conditions in which both the oil and the gas have to be stored in such storage tanks are quite specific and, consequently, the materials used for their construction present very high costs. In turn, due to safety matters, such pools surrounding each of the tanks are built, leading to an additional cost. To this, the costs for the periodic controls carried out are added, as well as the facilities maintenance, more particularly the storage tanks, which generate high costs for the use of heavy machinery and time loss, which could be used to optimize production. So, the purchase, assembly, installation and maintenance of the storage tanks generate high costs which very few companies may bear.
[0009] On the other hand, tanks which comprise big dimensions, store a great amount of oil and gas that may be dangerous in the event that they are not in optimal conditions, and due to various reasons, leaks or other types of drawbacks that occur endangering operators, the production zone and especially the environment.
[0010] Considering the current state of the art available for manifold batteries, it would be advantageous to have a new manifold battery, constituted and constructed to reduce the impact on the environment, the accidents, dangers and consequential risks of the flammable, toxic and damaging substances concentration, as well as the operative times and the connected costs.
[0011] Therefore, it is one of the purposes of the present invention to provide a new manifold battery which is constituted and constructed to reduce the impact on the environment, the accidents, dangers and consequential risks of the flammable, toxic and damaging substances concentration, as well as the operative times and the connected costs.
[0012] Another purpose of the present invention is to provide a manifold battery which reduces the costs, as well as, the generation, accumulation and release of gases, thus achieving a greater operative security.
[0013] Another purpose of the present invention is to provide a manifold battery which adjusts to the needs of individual circumstances, being able to adapt as a mobile battery to measure the wells, either in marginal, new or distant fields.
[0014] Still another purpose of the present invention is to provide a manifold battery that reduces the environmental impact.
SUMMARY
[0015] In keeping with one aspect of the present invention, a manifold battery for hydrocarbon fields includes an entrance manifold which connects to a plurality of separators, which are operatively interconnected through ducts and valve sets, with a disposition of gas storage devices and a set of circulating pumps. A purging chamber connects to the storage devices and separators. The manifold battery has three-way valves connected to at least a general line and at least a control line. The separators are connected to the general and control lines, and include at least two control separators and at least two general separators are connected among themselves, providing an auxiliary tank connected to those separators and to those circulating pumps through the respective ducts and valve sets, wherein one of the gas storage devices is a reserve gas vessel for instruments.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] For a better understanding and clarity of the present invention purpose, the same has been illustrated in a unique drawing, in which the invention has been represented in one of the preferred performance forms, all at the example title, where:
[0017] FIG. 1 shows a schematic diagram of the present manifold battery.
DETAILED DESCRIPTION
[0018] Referring to FIG. 1 , a new manifold battery for hydrocarbon fields is constituted and constructed to significantly reduce adverse impact on the environment, avoid gas accumulation which may endanger the facility and operators, and particularly reduce the operative costs and times.
[0019] The manifold battery for hydrocarbon fields of the present invention includes an entrance collector or “manifold” 1 constituted by a three-way valve disposition which present at least a general line 1 A and at least two control lines 1 B and 1 C, being interconnected to a plurality of separators by means of an entrance valve set 2 A, 2 A′ and 2 A″ respectively. All the production of a determined field derives to such three-way valve disposition, where the complete production flows through the general line 1 A, while the control lines 1 B and 1 C are used to evaluate the individual production of a determined well.
[0020] The plurality of separators includes at least two general separators 3 A and at least two control separators 3 B. That is why the hydrocarbons coming from the manifold 1 through the general line 1 A pass through the entrance valves 2 A and enter the general separators 3 A, while the hydrocarbons flowing through the control lines 1 B and 1 C, pass through the valves 2 A′ and 2 A″ respectively, and enter the control separators 3 B. In the general 3 A and control 3 B separators, hydrocarbons are separated by decantation, remaining in the liquid phase in the bottom zone of them, while the gaseous phase is in the upper one. Once the general 3 A and control 3 B separators have accumulated a pre-established level, the opening of one of the control 2 B valves occurs for the case of separators 3 A, and of one of the control valves 2 B′ and 2 B″ for the case of 3 B separators, respectively, so as to send the fluid to a discharge line 4 , towards a circulating pump set 5 . In addition, the gas is evacuated from a set of exit valves 2 C in the case of general separators 3 A, while it is evacuated from control separators 3 B by a set of exit valves 2 C′ and 2 C″, towards a gas storage disposition device.
[0021] Referring again to the circulation pumps 5 , the same comprise a first operation pump 5 A and a second auxiliary pump 5 B, where both circulating pumps are the type comprising a double effect piston, with a flow of at least 185 m3/h minimum at a maximum labor pressure of 75 kg/cm2, and a minimum suction pressure of at least 1 Kg/cm2. The circulating pump 5 A operates in a constant manner, evacuating the production, while, such circulation pump 5 B begins operating when pump 5 A is under preventive maintenance and/or under eventual fault.
[0022] In regards to the gas storage devices, they include a gas separator 6 which allows the elimination of the liquid existing in the gas coming from the separators 3 A and 3 B, a burning ditch 6 A and a reserve gas vessel for instruments 6 B which feeds the facility instruments with gas. That is how gas evacuates from the separators 3 A and 3 B, passes primarily through a gas measuring bridge, and then resides in the gas separator 6 and/or in the burning ditch 6 A and/or in the reserve gas vessel 6 B.
[0023] The excess gas is evacuated and directed to related motor compressor stations or treatment plants by means of a valve 6 C. In addition, the mentioned gas measuring bridge has a first pneumatic valve 6 D and a second pneumatic relief or venting valve 6 E. The first valve 6 D is connected to the general gas separator 6 , while said second valve 6 E is connected to the burning ditch 6 A. The latter is activated in case the pressure is higher than that established in the event of the gas pipeline break.
[0024] It should be pointed out that the liquid that is separated from the gas within the gas separator 6 , is purged and discharged through a valve 6 F towards a purging chamber 7 , which receives all of the purges of all the process elements through the purging lines 4 A and which have an emergency pool and a level indicator. Generally, the gas captured in the batteries is for consumption, as heater fuel, explosion motors, instrument gas, while the excess gas is destined for sale.
[0025] The manifold battery is provided with an auxiliary tank 8 connected to the separators 3 A and 3 B, and to the circulation pumps 5 A and 5 B, through the respective ducts and valve sets, where it has at least one entrance valve 8 A, a pneumatic control valve 8 B, at least an overflow pipe 11 and a pneumatic controller configured with a pressure lower than the separators' working pressure. It is then that, in the case of fault in the facility, either by the separators or by the pumps, the hydrocarbon production enters the tank 8 , through the entrance valve 8 A which is activated by the pneumatic controller. When such production reaches a determined level within the tank 8 , it sends a signal to a remote terminal unit “RTU”, which controls the opening of the pneumatic valve 8 B and the closing of a pneumatic valve located between the pumps 5 A and 5 B. The remote terminal unit RTU is of the type that performs the collection of the information supplied by the sensors connected to the process, the command of final control elements and the communication with a control center. Thus, pump 5 B starts operating so that it evacuates the tank production 8 . On reaching a vacuum pre-established height level, it should close the pneumatic valve 8 B and stop pump 5 B. In the event that the tank 8 overflows, there is an overflowing pipe 11 provided with a pneumatic valve and a level sensor which opens and evacuates the production to the purging chamber 7 through the purging line 4 A, avoiding in this way leaks in the facility zones and the consequential environmental impact.
[0026] On the other hand, each general separator 3 A has a level sensor 12 which acts when the interface level exceeds the point established activating the entrance pneumatic valve 2 A, closing and diverting the production to the other general separator 3 A. Moreover, it has a pressure sensor 13 which acts when the working pressure declines, activating the entrance pneumatic valve 2 A so that it closes and directs the production to the other general separator 3 A. In the event of fault in both general separators 3 A, either by level or by pressure, production is diverted to the tank 8 through a relief valve 10 that acts by pressure. In fact, each control separator 3 B also has a level sensor 14 which acts when the interface level exceeds the established point, activating a three way pneumatic valve which delivers the production through the individual line and through the general separators 3 A entrance. It also has a pressure sensor 15 which, when the separator working pressure 3 B is under the established point, activates the three way pneumatic valve closing the same, passing the production by individual line and by general separators entrance line. It may be pointed out that each of the separators 3 A and 3 B are provided with a level controller 16 , a sensor and pressure transmitter 17 and principally with a continuous level controller 18 , which prevents the pumps 5 A or 5 B from working in fault or being stopped due to fault of a minimum flow. In the event that all of the general separators 3 B and control separators 3 B start working in fault, control separators 3 B production is diverted through valves 2 A′ and 2 A″ to the entrance line of the general separators 3 A and afterwards, starting from them, diverting to tank 8 through relief valve 10 .
[0027] It is thus that the hydrocarbons coming from the wells are primarily delivered to the battery through collector 1 which allows delivering them to different separators, having two control separators 3 B and two general separators 3 A, where the control separators 3 B allow determining the individual production of each well by mass sensor meters. In the general separators 3 A, the general production is passed and the liquid phase is separated from the gaseous phase by densities difference, where the gaseous phase is directed to the gas pipeline or gas separator 6 and the liquid phase is discharged to a suction pipe or discharge line 4 which otherwise goes directly to pumps 5 A or 5 B, which send the previously separated oil to the crude treatment plant.
[0028] Thus, the manifold battery of the present invention reduces the impact to the environment, preventing gas accumulation which may endanger the facility or the operators, due to the fact that it prevents the use of the usual storage tanks in the traditional batteries, reduces the purchase, assembly and maintenance costs, and notoriously optimizes the operative times. | A manifold battery for hydrocarbon fields has an entrance manifold which is connected to a plurality of separators which are operatively connected through ducts and valve sets, with gas storage devices and a pair of circulating pumps. A purging chamber is also provided which is connected to the storage devices and to the separators. An auxiliary tank reduces the adverse impact to the environment, accidents, dangers and consequential risks of flammable, toxic and damaging substances concentration, as well as reducing the operative times and the related costs. | 8 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of the following U.S. Provisional Application No. 61/248,338, filed Oct. 2, 2009, the entire contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
Field of the Invention
[0002] This invention relates to the use of various 2-oxothiazole or 2-oxooxazole compounds for use in the prevention or treatment of chronic inflammatory disorders such as glomerulonephritis, rheumatoid arthritis and psoriasis. The invention also relates to certain new 2-oxothiazole or 2-oxo-oxazole compounds, pharmaceutical compositions comprising said compounds and to new processes for the manufacture thereof.
[0003] Mammalian cells contain a large number of phospholipases that hydrolyse phospholipids in a structurally specific manner for production of a myriad of products, many of which have potent biological activity. There has been considerable interest in characterising these enzymes because of their role in production of lipid mediators of inflammation. Since the first studies 20 years ago showing that mammalian cells contain a cystolic calcium dependent phospholipase specific for arachidonic acid, an extensive amount of evidence has substantiated a primary role for cPLA 2 as the key enzyme that mediates the release of arachidonic acid for the production of eicosanoids.
[0004] The enzyme cPLA 2 contributes to the pathogenesis of a variety of diseases particularly those in which inflammation plays a primary role implicating a role for inflammatory lipid mediators in disease pathogenesis. The inhibition therefore of such lipase enzymes offers a potential therapy for inflammatory conditions in particular chronic inflammatory conditions such as those above, psoriasis and glomerulonephritis.
[0005] The phospholipases are a group of enzymes that release unsaturated fatty acids from the sn2 position of membrane phospholipids. Once released, the fatty acids are converted by various enzymes into biologically very important signalling molecules. Release of arachidonate initiates the arachidonate cascade leading to the synthesis of eicosanoids such as prostaglandins.
[0006] Eicosanoids are important in a variety of physiological processes and play a central role in inflammation. In Inflammation, Vol. 18, No. 1 1994, Andersen et al identify the presence of certain phospholipases in psoriatic human skin.
[0007] It is therefore believed that inhibition of phospholipase enzymes should have potential in curing some of the inflammatory symptoms, including epidermal hyperproliferation due to increased leukotriene production, related to eicosanoid production and cell activation in both epidermis and dermis in psoriasis.
[0008] Psoriasis is a common, chronic, inflammatory skin disorder. Psoriatic tissue is characterised by chronic inflammation in both epidermis and dermis, the disease being further characterised by hyperplasia of epidermal keratinocytes, fibroblast activation, alteration of eicosanoid metabolism, and leukocyte infiltration.
[0009] Glomerulonephritis, also known as glomerular nephritis, abbreviated GN, is a renal disease characterized by inflammation of the glomeruli, or small blood vessels in the kidneys. It may present with isolated hematuria and/or proteinuria or as a nephrotic syndrome, acute renal failure, or chronic renal failure. Glomerulonephritis is categorised into several different pathological patterns, which are broadly grouped into non-proliferative or proliferative types.
[0010] The glomerulus is a unique vascular network with three specialised types of cell: the endothelial cell, the mesangial cell and the visceral epithelial cell
[0000] Mesangial cells (MC) serve a number of functions in the renal glomerular capillary including structural support of the capillary tuft, modulation of the glomerular hemodynamics and a phagocytic function allowing removal of macromolecules and immune complexes. The proliferation of MC is a prominent feature of glomerular disease including IgA nephropathy, membranoproliferative glomerulonephritis, lupus nephritis, and diabetic nephropathy.
[0011] Reduction of MC proliferation in glomerular disease models by treatment with, for example, a low protein diet has been shown to produce extracellular matrix expansion and glomerulosclerotic changes. MC proliferation inhibitors may therefore offer therapeutic opportunities for the treatment of proliferative glomerular disease.
[0012] Mesangial proliferative glomerulonephritis is a form of glomerulonephritis which involves inflammation at the kidney glomeruli. The mesangial cells which are a part of the glomerular capillaries increase in size giving the glomeruli a lumpy appearance. The disorder usually causes nephritic syndrome which represents protein loss in the urine. It may be present as acute, chronic or rapidly progressive glomerulonephritis and may progress to chronic renal failure.
[0013] The present inventors seek new treatments for, inter alia, chronic inflammatory conditions such as GN and psoriasis.
SUMMARY OF THE INVENTION
[0014] The present inventors have surprisingly found that certain 2-oxo-thiazoles or 2-oxo-oxazoles are ideal cPLA 2 inhibitors and offer new therapeutic routes to the treatment of chronic inflammatory disorders.
[0015] 2-oxothiazole type structures are not new. In Bioorganic and Medicinal Chemistry 16 (2008) 1562-1595, there is a review of chemistry in this field. 2-oxo (benz)thiazoles carrying peptides or amino acids on the 2-position (i.e. where the 2-oxo group forms part of the backbone of an amino acid) are known in the art as thrombin inhibitors.
[0016] Also reported are certain hydrolase and transferase inhibitors in particular having a 2-oxo-oleyl side chain. Similar compounds as fatty acid amide hydrolase inhibitors are reported in J Med Chem Vol. 51, No. 237329-7343. Their potential as inhibitors of cPLA 2 is not discussed.
[0017] A wider variety of 2-oxo-oxazole compounds are known from these papers. The majority of these compounds are either unsubstituted oxazole rings or they carry substituents in the position adjacent the oxygen atom. Their potential as inhibitors of cPLA 2 is not discussed.
[0018] Never before therefore, have the compounds claimed herein been identified as potential inhibitors of phospholipase enzymes and hence no link with chronic inflammatory conditions has been made.
[0019] Thus, viewed from one aspect the invention provides a compound of formula (I)
[0000]
[0020] wherein X is O or S;
[0021] R 1 is H, OH, SH, nitro, NH 2 , NHC 1-6 alkyl, N(C 1-6 alkyl) 2 , halo, haloC 1-6 alkyl, CN, C 1-6 -alkyl, OC 1-6 alkyl, C 2-6 -alkenyl, C 3-10 cycloalkyl, C 6-10 aryl, C 1-6 alkylC 6-10 aryl, heterocyclyl, heteroaryl, CONH 2 , CONHC 1-6 alkyl, CON(C 1-6 alkyl) 2 , OCOC 1-6 alkyl, C 1-6 alkylCOOH, C 1-6 alkylCOOC 1-6 alkyl or is an acidic group, such as a group comprising a carboxyl, phosphate, phosphinate, sulfate, sulfonate, or tetrazolyl group;
[0022] R 2 is as defined for R 1 or R 1 and R 2 taken together can form a 6-membered aromatic ring optionally substituted by up to 4 groups R 5 ;
[0023] R 3 is H, halo (preferably fluoro), or CHal 3 (preferably CF 3 ),
[0024] each R 5 is defined as for R 1 ;
[0025] V 1 is a covalent bond or a C 1-20 alkyl group, or C 2-20 -mono or multiply unsaturated alkenyl group; said alkyl or alkenyl groups being optionally interupted by one or more heteroatoms selected from O, NH, N(C 1-6 alkyl), S, SO, or SO 2 ;
[0026] M 1 is absent or is a C 5-10 cyclic group or a C 5-15 aromatic group (e.g. C 6-14 aromatic group); and
[0027] R 4 is H, halo, OH, CN, nitro, NH 2 , NHC 1-6 alkyl, N(C 1-6 alkyl) 2 , haloC 1-6 alkyl, a C 1-20 alkyl group, or C 2-20 -mono or multiply unsaturated alkenyl group, said C 1-20 alkyl or C 2-20 alkenyl groups being optionally interupted by one or more heteroatoms selected from O, NH, N(C 1-6 alkyl), S, SO, or SO 2 ;
[0028] with the proviso that the group V 1 M 1 R 4 as a whole provides at least 4 backbone atoms from the C(R 3 ) group;
[0029] or a salt, ester, solvate, N-oxide, or prodrug thereof;
[0030] for use in the treatment of a chronic inflammatory condition.
[0031] Viewed from another aspect the invention provides a compound of formula (II)
[0000]
[0032] wherein R 1 , R 2 , R 3 , R 5 and R 4 M 1 V 1 are as hereinbefore defined;
[0033] or a salt, ester, solvate, N-oxide, or prodrug thereof;
[0034] with the proviso that R 4 M 1 V 1 C(R 3 ) is not oleyl.
[0035] Viewed from another aspect the invention provides a compound of formula (III)
[0000]
[0036] wherein R 6 is H, C 1-6 alkyl, COOH, COOC 1-6 alkyl, CONH 2 , CONHC 1-6 alkyl, CON(C 1-6 alkyl) 2 , C 1-6 alkylCOOH, C 1-6 alkylCOOC 1-6 alkyl;
[0037] R 7 is H;
[0038] wherein R 3 is as hereinbefore defined;
[0039] V 1 is a covalent bond or a C 1-20 alkyl group, or C 2-20 -mono or multiply unsaturated alkenyl group;
[0040] M 1 is a covalent bond or is a C 5-10 cyclic group or a C 5-10 aromatic group; and
[0041] R 4 is H, halo, OH, CN, nitro, NH 2 , NHC 1-6 alkyl, N(C 1-6 alkyl) 2 , haloC 1-6 alkyl, a C 1-20 alkyl group, or C 2-20 -mono or multiply unsaturated alkenyl group, said alkyl or alkenyl groups being optionally interupted by one or more heteroatoms selected from O, NH, N(C 1-6 alkyl), S, SO, or SO 2 ;
[0042] or a salt, ester, solvate, N-oxide, or prodrug thereof
[0000] with the proviso that R 4 M 1 V 1 C(R 3 ) is not oleyl or —(CH 2 ) 6 Ph.
[0043] Viewed from another aspect the invention provides a compound of formula (I′)
[0000]
[0000] wherein X is O or S;
[0044] R 1 is H, OH, SH, nitro, NH 2 , NHC 1-6 alkyl, N(C 1-6 alkyl) 2 , halo, haloC 1-6 alkyl, CN, C 1-6 -alkyl, OC 1-6 alkyl, C 2-6 -alkenyl, C 3-10 cycloalkyl, C 6-10 aryl, C 1-6 alkylC 6-10 aryl, heterocyclyl, heteroaryl, CONH 2 , CONHC 1-6 alkyl, CON(C 1-6 alkyl) 2 , OCOC 1-6 alkyl, C 1-6 alkylCOOH, C 1-6 alkylCOOC 1-6 alkyl or is an acidic group, such as a group comprising a carboxyl, phosphate, phosphinate, sulfate, sulfonate, or tetrazolyl group;
[0045] R 2 is as defined for R 1 or R 1 and R 2 taken together can form a 6-membered aromatic ring optionally substituted by up to 4 groups R 5 ;
[0046] each R 3′ is the same or different and is H, C 1-6 alkylCOOR a where R a is H or C 1-6 alkyl, halo (preferably fluoro), or CHal 3 (preferably CF 3 ),
[0047] each R 5 is defined as for R 1 ;
[0048] V 1′ is a covalent bond, —NHCOC 0-6 alkyl- (i.e. where NH is adjacent the CR 3′ group), a C 1-20 alkyl group, or C 2-20 -mono or multiply unsaturated alkenyl group; said alkyl or alkenyl groups being optionally interupted by one or more heteroatoms selected from O, NH, N(C 1-6 alkyl), S, SO, or SO 2 ;
[0049] M 1 is absent or is a C 5-10 cyclic group or a C 5-15 aromatic group (e.g. C 6-14 aromatic group); and
[0050] R 4 is H, halo, OH, CN, nitro, NH 2 , NHC 1-6 alkyl, N(C 1-6 alkyl) 2 , haloC 1-6 alkyl, a C 1-20 alkyl group, or C 2-20 -mono or multiply unsaturated alkenyl group, said C 1-20 alkyl or C 2-20 alkenyl groups being optionally interupted by one or more heteroatoms selected from O, NH, N(C 1-6 alkyl), S, SO, or SO 2 ;
[0051] with the proviso that the group V 1′ M 1 R 4 as a whole provides at least 4 backbone atoms from the C(R 3′ ) 2 group;
[0052] or a salt, ester, solvate, N-oxide, or prodrug thereof
[0053] with the proviso that R 4 M 1 V 1′ C(R 3′ ) 2 is not oleyl. It is also preferred if R 4 M 1 V 1′ C(R 3′ ) 2 is not CH 2 Ph.
[0054] The invention also concerns a compound of formula (I′) as hereinbefore defined but without the disclaimer for use in the treatment of a chronic inflammatory condition.
[0055] Viewed from another aspect the invention provides a compound of formula (III′)
[0000]
[0056] wherein R 5 , R 7 , R 3′ , V 1′ , M 1 , R 4 are as hereinbefore defined;
[0057] with the proviso that R 4 M 1 V 1 C(R 3 ) is not oleyl or —(CH 2 ) 6 Ph.
[0058] Viewed from another aspect the invention provides a pharmaceutical composition claim comprising a compound of formula (I′), (II), (III) or (III′) as hereinbefore defined.
[0059] Viewed from another aspect the invention provides a compound of formula (I′), (II), (III) or (III′) as hereinbefore defined for use in therapy.
[0060] Viewed from another aspect the invention provides use of the a compound of formula (I) or (I′) as hereinbefore defined in the manufacture of a medicament for the treatment of a chronic inflammatory condition.
[0061] Viewed from another aspect the invention provides a method of treating a chronically inflammatory disorder comprising administering to a patient an effective amount of a compound of formula (I) or (I′) as hereinbefore defined.
DEFINITIONS
[0062] In this specification, unless stated otherwise, the term “alkyl” includes both straight and branched chain alkyl radicals and may be methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, t-pentyl, neo-pentyl, n-hexyl or i-hexyl, t-hexyl.
[0063] The term “cycloalkyl” refers to an optionally substituted carbocycle containing no heteroatoms, including mono-, and multicyclic saturated carbocycles, as well as fused ring systems. Cycloalkyl includes such fused ring systems as spirofused ring systems. Examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
[0064] The term “alkenyl” includes both straight and branched chain alkenyl radicals. The term alkenyl refers to an alkenyl radicals one or more double bonds and may be, but is not limited to vinyl, allyl, propenyl, i-propenyl, butenyl, i-butenyl, crotyl, pentenyl, i-pentenyl and hexenyl.
[0065] The term “aryl” refers to an optionally substituted monocyclic or bicyclic hydrocarbon ring system containing at least one unsaturated aromatic ring. Examples and suitable values of the term “aryl” are phenyl, naphtyl, 1,2,3,4-tetrahydronaphthyl, indyl, indenyl and the like.
[0066] In this specification, unless stated otherwise, the term “heteroaryl” refers to an optionally substituted monocyclic or bicyclic unsaturated, aromatic ring system containing at least one heteroatom selected independently from N, O or S. Examples of “heteroaryl” may be, but are not limited to thiophene, thienyl, pyridyl, thiazolyl, isothiazolyl, furyl, pyrrolyl, triazolyl, imidazolyl, oxadiazolyl, oxazolyl, isoxazolyl, pyrazolyl, imidazolonyl, oxazolonyl, thiazolonyl, tetrazolyl and thiadiazolyl, benzoimidazolyl, benzooxazolyl, benzothiazolyl, tetrahydrotriazolopyridyl, tetrahydrotriazolopyrimidinyl, benzofuryl, thionaphtyl, indolyl, isoindolyl, pyridonyl, pyridazinyl, pyrazinyl, pyrimidinyl, quinolyl, phtalazinyl, naphthyridinyl, quinoxalinyl, quinazolyl, imidazopyridyl, oxazolopyridyl, thiazolopyridyl, pyridyl, imidazopyridazinyl, oxazolopyridazinyl, thiazolopyridazinyl, cynnolyl, pteridinyl, furazanyl, benzotriazolyl, pyrazolopyridinyl, purinyl and the like.
[0067] In this specification, unless stated otherwise, the term “heterocycle” refers to an optionally substituted, monocyclic or bicyclic saturated, partially saturated or unsaturated ring system containing at least one heteroatom selected independently from N, O and S, e.g. piperidinyl, morpholino, or piperazinyl.
[0068] Any cyclic group can be a cycloalkyl group, cycloalkenyl group or heterocyclic group.
[0069] Any aromatic group can be aryl or heteroaryl in nature, e.g. phenyl, naphthyl or pyridyl.
[0070] An acidic group is one comprising a carboxyl, phosphate, phosphinate, sulfate, sulfonate, or tetrazolyl group, e.g. an C 1-6 alkyl linked to a carboxyl, phosphate, phosphinate, sulfate, sulfonate, or tetrazolyl group. Highly preferred acidic groups are COOH, COOC 1-6 alkyl, or C 1-6 alkyl substituted by COOH, COOC 1-6 alkyl or C 6-10 aryl group substituted by COOH, COOC 1-6 alkyl.
DETAILED DESCRIPTION OF INVENTION
[0071] It is preferred if X is S and the ring system is a thiazole system.
[0072] It is preferred if R 1 is hydrogen.
[0073] It is preferred if R 2 is hydrogen or is an acidic group, e.g. a group comprising a carboxylic group or derivative thereof (i.e. a COO group). Thus, R 2 may be COOH, or an ester, e.g. alkyl ester thereof. The acid group may also be spaced apart from the ring by some form of linking chain such as an alkylene chain or an aromatic group. Highly preferred groups are COOH, COOC 1-6 alkyl and C 1-6 alkylCOOH.
[0074] It is believed that the presence of a carboxyl functional group attached to the heterocyclic ring enhances interaction of the compound with the active site of the phospholipase enzyme, in particular, the side chain of arginine 200. This arginine is believed to carry a free guanidine group so any substituent which can favourably interact with this guanidine is preferred at the R 1 and/or R 2 position.
[0075] In one embodiment R 1 and R 2 can be taken together to form a ring system such as a phenyl ring or pyridine ring. Where a pyridine ring system forms the N atom is preferably in the 4-position of the ring (S=1 position, N=3, N=4). Preferably the ring system will be a carbon ring system, e.g. forming a benzothiazole type structure. If such a ring system is formed, it may be substituted preferably by 1 or 2 groups R 5 . Preferences for R 5 are the same as those for R 2 . Preferably the R 5 group is positioned on the 5-position of the ring (where S is the 1-position and N is the 3-position). Ideally however such a ring system is unsubstituted.
[0076] Preferred compounds in this regard are of formula (VII)
[0000]
[0077] where the substituents are as hereinbefore defined and Z is C or N.
[0078] It is especially preferred if at least one of R 1 and R 2 (especially R 1 ) is hydrogen. The heterocyclic ring is ideally only monosubstituted. In a further preferred embodiment both R 1 and R 2 are hydrogen.
[0079] R 3 is preferably hydrogen or, in a highly preferred embodiment, R 3 is halo, especially fluoro. It is believed that the presence of the F atom adjacent the carbonyl enhances the activity of the carbonyl group and may also interact favourably with the active site in the cPLA 2 enzyme, in particular IVa PLA 2 .
[0080] It is preferred if one R 3 is H. It is also preferable if one R 3 is halo, especially fluoro. The presence of two fluoro atoms as R 3 , is also preferred. It is believed that the presence of the F atom adjacent the carbonyl enhances the activity of the carbonyl group and may also interact favourably with the active site in the cPLA 2 enzyme, in particular IVa PLA 2 .
[0081] The discussion of the group V 1 M 1 R 4 which follows also applies to V 1′ M 1 R 4 . The group V 1 M 1 R 4 as a whole provides at least 4 backbone atoms from the C(R 3 ) group. Preferably, V 1 M 1 R 4 provides at least 5 backbone atoms, more preferably at least 7 backbone atoms especially at least 10 backbone atoms from the C(R 3 ) group. For the avoidance of doubt, where there is an aromatic group in the backbone, the backbone is considered to follow the shortest route around the ring. Thus, for a 1,4-phenyl group, that would constitute 4 backbone atoms. A 1,3 linked 5 membered ring in the backbone would constitute 3 backbone atoms and so on.
[0082] V 1 (or V 1′ ) is preferably an C 1-15 -alkyl group, C 2-20 -alkenyl group or is a —C 1-6 alkylO— group (i.e. where the O atom bonds to M 1 ). Any alkenyl group can have one or more than one double bond. Where more than one double bond is present, it is preferred if these are non conjugated. Double bonds will preferably take the cis form. Preferred alkyl groups for V 1 or (V 1′ ) include C 1-6 -alkyl.
[0083] It is especially preferred if any alkyl or alkenyl group in V 1 or V 1′ ) is linear.
[0084] V 1′ may also represent an amide linkage NHCO which may then optionally carry an alkyl chain of up to 6 carbon atoms. That chain is preferably linear. The NH part of the linkage is adjacent the CR 3′ group.
[0085] Preferably M 1 is either absent or is an C 6-10 aryl group, especially a phenyl group. Alternatively, M 1 may be a bicyclic aromatic group such as decalin. A further preferred embodiment is where M 1 represents a biphenyl group, i.e. a C 5-15 aromatic group in which two phenyl groups are directly linked. Where M 1 is a phenyl group, V 1 or V 1′ and R 4 are preferably attached in the 1 and 4 positions of the ring, i.e. they are para to each other.
[0086] R 4 is preferably an H atom, C 1-10 alkyl group or an C 1-10 alkoxy group.
[0087] In one embodiment it is preferred in any compound of the invention that R 4 M 1 V 1 C(R 3 ) or R 4 M 1 V 1′ C(R 3′ ) 2 is not oleyl or —(CH 2 ) 6 Ph.
[0088] Thus, a still more preferred compound of the invention is of formula (VI)
[0000]
[0089] wherein R 1 is H;
[0090] R 2 is H, COOH, COOC 1-6 alkyl, C 1-6 alkylCOOH, or C 1-6 alkylCOOC 1-6 alkyl;
[0091] R 3 is H or F;
[0092] V 1 is C 1-15 -alkyl group, C 2-20 -alkenyl group or is a —C 1-6 -alkylO— group;
[0093] M 1 is absent or is a phenyl group;
[0094] R 4 is H, C 1-10 alkyl group or an C 1-10 alkoxy group.
[0095] In further highly preferred combinations:
[0000] 1. V 1 is C 1-15 -alkyl group or C 2-20 -alkenyl group, M 1 is absent and R 4 is H.
2. V 1 is C 1-6 -alkyl group or is a —C 1-6 -alkylO group, M 1 is a phenyl group, and R 4 is H or C 1-6 alkoxy (where the O atom is adjacent the M 1 group);
3. R 4 V 1 M 1 represents a C 10-20 linear alkyl group.
[0096] Also preferred are options 1-3 above in which V 1 is V 1′ .
[0097] In a highly preferred embodiment, the invention provides the compounds in the examples.
Synthesis
[0098] The manufacture of the compounds of the invention typically involves known literature reactions. For example, the formation of an 2-oxothiazole, the precursor to many of the claimed compounds, can be achieved by reaction of an aldehyde XCOH with thiazole in the presence of a base and subsequent oxidation of the hydroxyl to a ketone. The X group is obviously selected to form the desired R 4 M 1 V 1 or R 4 M 1 V 1′ group or a precursor thereof.
[0099] These reactions are summarised in Scheme 1 below.
[0000]
[0100] It will be appreciated that in the scheme above and many of those below, specific reagents and solvents may mentioned to aid the skilled man in carrying out the reactions described. The skilled man will appreciate however that a variety of different conditions, reagents, solvents, reactions etc could be used to effect the chemistry described and the conditions quoted are not intended to be limiting on the reactions described.
[0101] An alternative strategy involves the reaction of an alkoxy amide XCON(Oalkyl) with thiazole in base which affords 2-oxothiazoles directly. This reaction is summarised in scheme 2.
[0000]
[0102] The inventors have however found a new and preferred way of forming 2-oxothiazoles and this forms a still yet further aspect of the invention. The new process involves the reaction of an oxo-morpholino structure with thiazole, typically in the presence of a base. This reaction affords 2-oxo thiazoles directly and is a new reaction.
[0103] Thus viewed from another aspect the invention provides a process for the formation of a 2-oxothiazole comprising reacting a compound of formula (IV)
[0000]
[0104] wherein Y is an organic group, e.g. a group R 4 M 1 V 1 CH(R 3 ),
[0105] with an optionally substituted thiazole in the presence of a base so as to form an optionally substituted compound of formula (V)
[0000]
[0106] This reaction is effected in the presence of a base, e.g. nBuLi or the like. Ideally, the reaction is effected at low temperature, e.g. at 0° C. or below so in an ice bath, or other known cooling system, e.g. liquid ammonia.
[0107] It will be appreciated that this reaction is preferably used to form compounds of formula (I) or (II) or (III) or their (I′)/(III′) analogues and this forms a still further aspect of the invention. It will be preferred therefore if the definition if Y reflects the group R 4 M 1 V 1 CH(R 3 ) or R 4 M 1 V 1′ C(R 3′ ) 2 or forms a precursor thereto. It will also be preferred if the thiazole used reflects the preferred thiazole reactant required to make a compound of the invention, i.e. carrying the necessary R 1 /R 2 substituents etc. The reaction is however more generally applicable so variable Y is broadly defined and the thiazole may be optionally substituted.
[0108] It is believed that the morpholino intermediates used in this reaction are new and these form a further aspect of the invention. Thus, viewed from another aspect the invention provides an intermediate compound of formula (IX)
[0000]
[0109] wherein R 4 M 1 V 1 CH(R 3 ) is as hereinbefore defined.
[0110] Viewed from another aspect the invention provides an intermediate compound of formula (IX′)
[0000]
[0111] wherein R 4 M 1 V 1′ C(R 3 ) 2 is as hereinbefore defined.
[0112] There are still further ways of developing a 2-oxo thiazole ring carrying a substituent. The ring itself can be generated from a thioamide as described in scheme 3.
[0000]
[0113] As noted above, an interesting class of compounds of the invention are those having a fluoro atom adjacent the carbonyl. This is conveniently introduced before attachment of the ring system by conventional chemistry. A hydroxy group may be converted to a fluoro group using Diethylaminosulfur trifluoride (DAST) for example. This chemistry is elucidated below:
[0000]
[0114] The formed compound can react with thiazole as described above.
[0000] Variations of the substituents on the heterocyclic rings and manipulation of the side chain binding the carbonyl can be achieved using all manner of synthetic techniques which the skilled man will know. Guidance is offered in the examples as to how to make a wide variety of compounds and the principles described can be extended to the compounds encompassed by the claims.
[0115] The principles described above for preparing thiazoles can be extended to the oxazole species.
Intermediates
[0116] Various intermediates are also new and form a further aspect of the invention. In particular, the invention covers the reduced analogue of the final 2-oxoheterocycle, i.e. a 2-hydroxy analogue. Thus, viewed from another aspect the invention provides a compound of formula (VIII)
[0000]
[0000] wherein R 1 , R 2 , R 3 , R 3′ , R 5 and R 4 M 1 V 1 /R 4 M 1 V 1′ are as hereinbefore defined;
[0117] or a salt, ester, solvate, N-oxide, or prodrug thereof;
[0118] preferably with the proviso that R 4 M 1 V 1 C(R 3 ) or R 4 M 1 V 1 C(R 3 ) 2 is not oleyl.
Chronic Inflammatory Disorders
[0119] The compounds of the invention are used in the treatment of chronic inflammatory disorders, in particular those associated with phospholipase inhibition.
[0120] Preferably, any compound of the invention will achieve 90% inhibition against IVa PLA 2 .
[0121] Preferably, compounds of the invention inhibit IVa cPLA 2 at a low μM range such as 5 μM or less, preferably 4 μM or less.
[0122] It is further preferred that the compounds of the invention show greater inhibition of IVa cPLA 2 than iPLA 2 or sPLA 2 according to published assays for these enzymes (see, for example, Yang, H et al. (1999) Anal. Biochem. 269: 278). Ideally, the compounds of the invention show limited or no inhibition of iPLA 2 or sPLA 2 and they are therefore highly specific for the IVa cPLA 2 enzyme.
[0123] Specific diseases of interest are glomerulonephritis, inflammatory dermatoses such as psoriasis and rheumatoid arthritis.
[0124] Further conditions of interest include other inflammatory dermatoses such as atopic dermatitis, allergic contact dermatitis, seborrheic dermatitis, pityriasis rosea , lichen planus and drug eruptions.
[0125] Furthermore the compounds of the invention may have use in the treatment of other types of arthritis and dermatoses, inflammatory CNS diseases, multiple sclerosis, chronic obstructive pulmonary disease, chronic lung inflammatory conditions, inflammatory bowel disease such as ulcerative colitis and crohns disease and cardiovascular disease.
[0126] Thus viewed from a further aspect the invention provides for the treatment of any of the conditions listed above using the compounds of the invention.
Formulation
[0127] The compounds of the invention are preferably formulated as pharmaceutically acceptable compositions. The phrase “pharmaceutically acceptable”, as used in connection with compositions of the invention, refers to molecular entities and other ingredients of such compositions that are physiologically tolerable and do not typically produce untoward reactions when administered to a mammal (e.g. human). Preferably, as used herein, the term “pharmaceutically acceptable” means approved by a regulatory agency of the Federal or a state government or listed in the U.S. Pharmacopoeia or other generally recognized pharmacopoeia for use in mammals, and more particularly in humans.
[0128] The term “carrier” applied to pharmaceutical compositions of the invention refers to a diluent, excipient, or vehicle with which an active compound is administered. Such pharmaceutical carriers can be sterile liquids, such as water, saline solutions, aqueous dextrose solutions, aqueous glycerol solutions, and oils, including those of petroleum, animal, vegetable or synthetic origin, such as peanut oil, soybean oil, mineral oil, sesame oil and the like. Suitable pharmaceutical carriers are described in “Remington's Pharmaceutical Sciences” by E. W. Martin, 18th Edition, incorporated by reference. Particularly preferred for the present invention are carriers suitable for immediate-release, i.e., release of most or all of the active ingredient over a short period of time, such as 60 minutes or less, and make rapid absorption of the drug possible.
[0129] The compounds of the invention can be administered in salt, solvate, prodrug or ester form, especially salt form. Typically, a pharmaceutical acceptable salt may be readily prepared by using a desired acid. The salt may precipitate from solution and be collected by filtration or may be recovered by evaporation of the solvent. For example, an aqueous solution of an acid such as hydrochloric acid may be added to an aqueous suspension of a compound of formula (I) and the resulting mixture evaporated to dryness (lyophilised) to obtain the acid addition salt as a solid. Alternatively, a compound of formula (I) may be dissolved in a suitable solvent, for example an alcohol such as isopropanol, and the acid may be added in the same solvent or another suitable solvent. The resulting acid addition salt may then be precipitated directly, or by addition of a less polar solvent such as diisopropyl ether or hexane, and isolated by filtration.
[0130] Suitable addition salts are formed from inorganic or organic acids which form non-toxic salts and examples are hydrochloride, hydrobromide, hydroiodide, sulphate, bisulphate, nitrate, phosphate, hydrogen phosphate, acetate, trifluoroacetate, maleate, malate, fumarate, lactate, tartrate, citrate, formate, gluconate, succinate, pyruvate, oxalate, oxaloacetate, trifluoroacetate, saccharate, benzoate, alkyl or aryl sulphonates (eg methanesulphonate, ethanesulphonate, benzenesulphonate or p-toluenesulphonate) and isethionate. Representative examples include trifluoroacetate and formate salts, for example the bis or tris trifluoroacetate salts and the mono or diformate salts, in particular the tris or bis trifluoroacetate salt and the monoformate salt.
[0131] Those skilled in the art of organic chemistry will appreciate that many organic compounds can form complexes with solvents in which they are reacted or from which they are precipitated or crystallized. These complexes are known as “solvates”. For example, a complex with water is known as a “hydrate”. Solvates of the compounds of the invention are within the scope of the invention. The salts of the compound of Formula (I) may form solvates (e.g. hydrates) and the invention also includes all such solvates.
[0132] The term “prodrug” as used herein means a compound which is converted within the body, e.g. by hydrolysis in the blood, into its active form that has medical effects.
[0133] The compounds of the invention are proposed for use in the treatment of, inter alia, chronic inflammatory disorders. By treating or treatment is meant at least one of:
[0000] (i). preventing or delaying the appearance of clinical symptoms of the disease developing in a mammal;
(ii). inhibiting the disease i.e. arresting, reducing or delaying the development of the disease or a relapse thereof or at least one clinical or subclinical symptom thereof, or
(iii). relieving or attenuating one or more of the clinical or subclinical symptoms of the disease.
[0134] The benefit to a subject to be treated is either statistically significant or at least perceptible to the patient or to the physician. In general a skilled man can appreciate when “treatment” occurs.
[0135] The word “treatment” is also used herein to cover prophylactic treatment, i.e. treating subjects who are at risk of developing a disease in question.
[0136] The compounds of the invention can be used on any animal subject, in particular a mammal and more particularly to a human or an animal serving as a model for a disease (e.g. mouse, monkey, etc.).
[0137] An “effective amount” means the amount of a compound that, when administered to an animal for treating a state, disorder or condition, is sufficient to effect such treatment. The “effective amount” will vary depending on the compound, the disease and its severity and the age, weight, physical condition and responsiveness of the subject to be treated and will be ultimately at the discretion of the attendant doctor.
[0138] While it is possible that, for use in the methods of the invention, a compound of formula I may be administered as the bulk substance, it is preferable to present the active ingredient in a pharmaceutical formulation, for example, wherein the agent is in admixture with a pharmaceutically acceptable carrier selected with regard to the intended route of administration and standard pharmaceutical practice.
[0139] The term “carrier” refers to a diluent, excipient, and/or vehicle with which an active compound is administered. The pharmaceutical compositions of the invention may contain combinations of more than one carrier. Such pharmaceutical carriers can be sterile liquids, such as water, saline solutions, aqueous dextrose solutions, aqueous glycerol solutions, and oils, including those of petroleum, animal, vegetable or synthetic origin, such as peanut oil, soybean oil, mineral oil, sesame oil and the like. Water or aqueous solution saline solutions and aqueous dextrose and glycerol solutions are preferably employed as carriers, particularly for injectable solutions. Suitable pharmaceutical carriers are described in “Remington's Pharmaceutical Sciences” by E. W. Martin, 18th Edition. The choice of pharmaceutical carrier can be selected with regard to the intended route of administration and standard pharmaceutical practice. The pharmaceutical compositions may comprise as, in addition to, the carrier any suitable binder(s), lubricant(s), suspending agent(s), coating agent(s), and/or solubilizing agent(s).
[0140] It will be appreciated that pharmaceutical compositions for use in accordance with the present invention may be in the form of oral, parenteral, transdermal, inhalation, sublingual, topical, implant, nasal, or enterally administered (or other mucosally administered) suspensions, capsules or tablets, which may be formulated in conventional manner using one or more pharmaceutically acceptable carriers or excipients.
[0141] There may be different composition/formulation requirements depending on the different delivery systems. Likewise, if the composition comprises more than one active component, then those components may be administered by the same or different routes.
[0142] The pharmaceutical formulations of the present invention can be liquids that are suitable for oral, mucosal and/or parenteral administration, for example, drops, syrups, solutions, injectable solutions that are ready for use or are prepared by the dilution of a freeze-dried product but are preferably solid or semisolid as tablets, capsules, granules, powders, pellets, pessaries, suppositories, creams, salves, gels, ointments; or solutions, suspensions, emulsions, or other forms suitable for administration by the transdermal route or by inhalation.
[0143] The compounds of the invention can be administered for immediate-, delayed-, modified-, sustained-, pulsed- or controlled-release applications.
[0144] In one aspect, oral compositions are slow, delayed or positioned release (e.g., enteric especially colonic release) tablets or capsules. This release profile can be achieved without limitation by use of a coating resistant to conditions within the stomach but releasing the contents in the colon or other portion of the GI tract wherein a lesion or inflammation site has been identified or a delayed release can be achieved by a coating that is simply slow to disintegrate or the two (delayed and positioned release) profiles can be combined in a single formulation by choice of one or more appropriate coatings and other excipients. Such formulations constitute a further feature of the present invention.
[0145] Pharmaceutical compositions can be prepared by mixing a therapeutically effective amount of the active substance with a pharmaceutically acceptable carrier that can have different forms, depending on the way of administration. Typically composition components include one or more of binders, fillers, lubricants, odorants, dyes, sweeteners, surfactants, preservatives, stabilizers and antioxidants.
[0146] The pharmaceutical compositions of the invention may contain from 0.01 to 99% weight—per volume of the active material. The therapeutic doses will generally be between about 10 and 2000 mg/day and preferably between about 30 and 1500 mg/day. Other ranges may be used, including, for example, 50-500 mg/day, 50-300 mg/day, 100-200 mg/day.
[0147] Administration may be once a day, twice a day, or more often, and may be decreased during a maintenance phase of the disease or disorder, e.g. once every second or third day instead of every day or twice a day. The dose and the administration frequency will depend on the clinical signs, which confirm maintenance of the remission phase, with the reduction or absence of at least one or more preferably more than one clinical signs of the acute phase known to the person skilled in the art.
[0148] It is within the scope of the invention for a compound as described herein to be administered in combination with another pharmaceutical, e.g. another drug with known efficacy against the disease in question. The compounds of the invention may therefore be used in combination therapy.
[0149] The invention will now be further described with reference to the following non limiting examples:
[0150] The chemistry described in the following schemes is used to manufacture the compounds described in the tables which follow. The starting materials in each scheme are readily available compounds. In general, molar equivalents of each reactant are employed.
[0151] The chemistry described in the following schemes is used to manufacture the compounds described in the tables which follow. The starting materials in each scheme are readily available compounds. In general, molar equivalents of each reactant are employed.
Experimental Procedures for the Formation of Compounds
[0000]
A. To a solution of thiazole (1.1 mmol) in dry THF (2 mL) under argon atmosphere and at −78° C., n-BuLi solution (1.1 mmol, 2.5 M in hexanes) was added dropwise over a period of 5 min. After stirring at −78° C. for 30 min, a solution of the appropriate aldehyde (1 mmol) in dry THF (2 mL) was added and the mixture was stirred for additional 4 hours at −78° C. Then, H 2 O was added and the mixture was extracted thrice with EtOAc. The organic layer was dried (Na 2 SO 4 ) and concentrated under reduced pressure. Purification by flash eluting with the appropriate mixture of EtOAc:petroleum ether (40-60° C.) afforded the desired product.
B. To a solution of the hydroxy-heterocycle (1 mmol) in dry CH 2 Cl 2 (10 mL), Dess-Martin periodinane was added (1.5 mmol) and the mixture was stirred for 1 h at rt. The organic solution was washed with 10% aqueous NaHCO 3 , dried over Na 2 SO 4 and concentrated under reduced pressure. The residue was purified by column-chromatography using the appropriate mixture of EtOAc:petroleum ether (40-60° C.) as eluent.
C. To a stirred solution of the carboxylic acid (1 mmol) in CH 2 Cl 2 (7 mL), 4-dimethylaminopyridine (DMAP) (1 mmol), N, O-dimethyl hydroxyamine hydrochloride (1 mmol), N-methylmorpholine (1 mmol) and N-(3-dimethylaminopropyl)-N′-ethyl carbodiimide hydrochloride (WSCI.HCl) (1 mmol) were added consecutively at room temperature. The reaction mixture was left stirring for 18 h. It was then washed with an aqueous solution of 10% citric acid (3×10 mL), brine (10 mL), an aqueous solution of NaHCO 3 5% (3×10 mL) and brine (10 mL). The organic layer was dried (Na 2 SO 4 ) and concentrated under reduced pressure. The amide was purified by flash chromatography eluting with the appropriate mixture of EtOAc:petroleum ether (40-60° C.) to afford the desired product.
D. To a stirred solution of acid (1 mmol) in dry CH 2 Cl 2 (7 mL), DMF (0.5 eq.) was added followed by oxalyl chloride (3 mmol) at room temperature. The reaction mixture was left stirring for 3 h. The solvent was removed and dry Et 2 O (7 mL) was added and cooled at 0° C. Pyridine (5 mmol) was added drop-wise, followed by drop-wise adittion of morpholine (5 mmol). The reaction mixture was left stirring for 18 h at room temperature. Then, H 2 O (8 mL) was added and it was left stirring for 30 min. The layers were separated and the organic layer was washed with an aqueous solution of HCl 1N (3×10 mL), brine (1×10 mL), an aqueous solution of NaHCO 3 5% (3×10 mL) and brine (1×10 mL). The organic layer was dried (Na 2 SO 4 ) and concentrated under reduced pressure. Purification by flash chromatography eluting with the appropriate mixture of EtOAc:petroleum ether (40-60° C.) afforded the desired product.
E. To a stirred solution of thiazole or benzothiazole (3 mmol) in dry Et 2 O (20 mL) at −78° C. under a dry argon atmosphere was added a solution of n-BuLi (1.6 M in hexanes, 3 mmol) drop-wise over a period of 10 min. The resulting orange solution was stirred for 45 min. Then, a solution of the amide (1 mmol) in dry Et 2 O (2 mL) was slowly added giving the mixture a dark brown color. After stirring for 30 min. at −78° C., the mixture was allowed to warm up to room temperature over a period of 2 h. Then, saturated aqueous ammonium chloride solution was added and the mixture was extracted with ether (2×10 mL). The combined extracts were washed with brine and then dried over Na 2 SO 4 and concentrated under reduced pressure. Purification by flash chromatography eluting with the appropriate mixture of EtOAc:petroleum ether (40-60° C.) afforded the desired product.
F. To a stirred solution of the ester (1 mmol) in dry Et 2 O (10 mL) was added dropwise DIBALH (1.1 mL, 1.0 M in hexane, 1.1 mmol) at 0° C. The reaction was stirred for 10 min and then quenched with H 2 O. The mixture was stirred for 30 min, dried over Na 2 SO 4 , and filtered through a pad of Celite. The solvent was evaporated and the crude product was purified by silica gel column chromatography.
G. To a solution of the alcohol (1 mmol) in a mixture of toluene-EtOAc (6 mL), a solution of NaBr (1.05 mmol) in water (0.5 mL) was added, followed by AcNH-TEMPO (0.01 mmol). To the resulting biphasic system, which was cooled at −5° C., an aqueous solution of 0.35 M NaOCl (3.14 mL, 1.10 mmol) containing NaHCO 3 (3 mmol) was added dropwise while stirring vigorously at −5° C. over a period of 1 h. After the mixture had been stirred for a further 15 min at 0° C., EtOAc (6 mL) and H 2 O (2 mL) were added. The aqueous layer was separated and washed with EtOAc (4 mL). The combined organic layers were washed consecutively with 5% aqueous citric acid (6 mL) containing 5% KI, 10% aqueous Na 2 S 2 O 3 (6 mL), and brine and dried over Na 2 SO 4 . The solvents were evaporated under reduced pressure, and the residue was used immediately in the next step without any purification.
H. A solution of the aldehyde (1 mmol) in CH 2 Cl 2 (2 mL) was added to a mixture of tert-butyl dimethylsilylcyanide (1 mmol), potassium cyanide (0.17 mmol) and 18-crown-6 (0.4 mmol) under argon atmosphere. The mixture was stirred for 1 h. The solvent was evaporated and the crude product was purified by silica gel column chromatography eluting with the appropriate mixture of EtOAc:petroleum ether (40-60° C.) to afford the desired product.
I. To a solution of the cyanide (1 mmol) in CH 2 Cl 2 (20 mL) at 0° C. was added 30% H 2 O 2 (0.5 mL), tetrabutyammonium hydrogen sulfate (0.2 mmol) and an aqueous solution of 0.5 N NaOH (1.2 mmol). The reaction mixture was stirred in a sealed flask for 18 h during which additional H 2 O 2 (0.5 mL) were added thrice. H 2 O and CH 2 Cl 2 were added and the organic layer was separated, washed with brine and dried over Na 2 SO 4 . The crude product was purified by silica gel column chromatography eluting with the appropriate mixture of EtOAc:petroleum ether (40-60° C.) to afford the desired product.
J. Lawesson's reagent (0.6 mmol) was added to a solution of the amide (1 mmol) in dry toluene (10 mL) under argon atmosphere. The reaction mixture was stirred for 18 h at room temperature. The solvent was evaporated and the crude product was purified by silica gel column chromatography eluting with the appropriate mixture of EtOAc:petroleum ether (40-60° C.) to afford the desired product.
K. To a solution of the thioamide (1 mmol) in ethanol (3.2 mL) under argon atmosphere, was added ethyl bromopyruvate or ethyl 4-chloroacetoacetate (1 mmol) and concentrated H 2 SO 4 (10 μL). The reaction mixture was stirred for 18 h. The solvent was evaporated and the crude product was purified by silica gel column chromatography eluting with the appropriate mixture of EtOAc:petroleum ether (40-60° C.) to afford the desired product.
L. To a solution of the hydroxyl heterocyclic ester (1 mmol) in EtOH (25 mL), an aqueous solution of 1 N NaOH (20 mmol, 20 mL) was added. After stirring for 1 h, the solution was acidified with aqueous solution of 1N HCl and the product was extracted with Et 2 O. The organic layer was separated, washed with brine and dried over Na 2 SO 4 . The product was used in the next step without any purification.
M. To a solution of the oxo heterocyclic ester (1 mmol) in EtOH (25 mL), an aqueous solution of 20% Cs 2 CO 3 (20 mmol, 20 mL) was added. After stirring for 18 h, the solution was acidified with aqueous solution of 1N HCl and the product was extracted with Et 2 O. The organic layer was separated, washed with brine and dried over Na 2 SO 4 . The product was purified by recrystallization.
N. To a stirred solution of LiAlH 4 (1M in THF, 2.9 mmol) in dry Et 2 O (5.5 mL) under argon atmosphere and at −20° C. a solution of the ester (1 mmol) in dry Et 2 O (5.5 mL) was added. The reaction was stirred for 20 min at −20° C. and for 20 min at rt. Then, it was cooled at 0° C. and quenched with H 2 O. The mixture was stirred for 30 min at rt. Then, additional H 2 O was added and the mixture was acidified with 1 N HCl to pH 5. The aqueous layer was washed twice with Et 2 O, and then the combined organic layers were washed with brine, dried over Na 2 SO 4 , and the solvent was evaporated. The crude product was purified by silica gel column chromatography eluting with the appropriate mixture of EtOAc:petroleum ether (40-60° C.) to afford the desired product.
O. To a stirred solution of the alcohol (1 mmol) in acetone (4.2 mL), K 2 CO 3 (3 mmol) was added followed by a catalytic amount of KI and the appropriate bromide (1.1 mmol). The solution was refluxed for 18 h, the solvent was evaporated, and H 2 O and EtOAc were added. The aqueous layer was washed twice with EtOAc and then the combined organic layers were washed with brine, dried over Na 2 SO 4 , and the solvent was evaporated. The crude product was purified by silica gel column chromatography eluting with the appropriate mixture of EtOAc:petroleum ether (40-60° C.) to afford the desired product.
P. A solution of the hydroxy compound (1 mmol) in dry CH 2 Cl 2 (50 mL) was treated dropwise with a solution of DAST (3 mmol) in dry CH 2 Cl 2 (2 mL) under argon atmosphere and at −78° C. The reaction mixture was stirred for 2 h at −78° C. and for additional 16 h at rt. Then, a saturated solution of NaHCO 3 was added until the bubbling of CO 2 stopped. The solution was stirred for 20 min and then H 2 O and CH 2 Cl 2 were added. The organic layer was separated, dried over Na 2 SO 4 , filtered and evaporated, and the crude product was purified by column chromatography on silica gel eluting with EtOAc-petroleum ether (bp 40-60° C.) to yield the desired fluoro derivative.
Q. A solution of oxalyl chloride (4 mmol) in dry CH 2 Cl 2 (3 mL) under argon atmosphere and at −60° C. was treated dropwise with a solution of dry DMSO (8 mmol) in dry CH 2 Cl 2 (3.5 mL). After 5 min, a solution of the fluoro alcohol (1 mmol) in dry CH 2 Cl 2 (20 mL) was added dropwise and after additional 15 min, dry Et 3 N (16 mmol) was added. The reaction mixture was stirred for 1 h to reach room temperature. Then, the reaction mixture was poured in ice and the aqueous layer was extracted thrice with CH 2 Cl 2 . The combined organic layers were washed with brine, dried over Na 2 SO 4 , and the solvent was evaporated. The crude product was purified by silica gel column chromatography eluting with the appropriate mixture of EtOAc:petroleum ether (40-60° C.) to afford the desired product.
R. A solution of the aldehyde (1 mmol) and methyl (triphenylphosphanylidene)acetate (1.1 mmol) in dry CH 2 Cl 2 (3 mL) under argon atmosphere was refluxed for 1 h and then left stirring for 16 h at rt. Saturated solution of NH 4 Cl was added and the aqueous layer was extracted thrice with CH 2 Cl 2 . The combined organic layers were washed with brine, dried over Na 2 SO 4 , and the solvent was evaporated. The crude product was purified by silica gel column chromatography eluting with the appropriate mixture of EtOAc:petroleum ether (40-60° C.) to afford the desired product.
S. A mixture of the unsaturated ester (1 mmol) in dry 1,4-dioxane (10 mL) and a catalytic amount of 10% palladium on activated carbon was hydrogenated for 18 h. After filtration through a pad of celite and the solvent was removed in vacuo. The crude product was purified by silica gel column chromatography eluting with the appropriate mixture of EtOAc:petroleum ether (40-60° C.) to afford the desired product.
T. A solution of the aldehyde (1 mmol) and NaHSO 3 (1.5 mmol in 1.3 mL H 2 O) in CH 2 Cl 2 (1.2 mL) was stirred for 30 min at room temperature. After the formation of a white salt, the organic solvent was evaporated and water (1 mL) was added. The mixture was cooled to 0° C. and an aqueous solution of KCN (1.5 mmol in 1.3 mL H 2 O) was added dropwise. The reaction mixture was stirred for another 18 h at room temperature and then CH 2 Cl 2 and water were added. The organic layer was washed with brine and dried (Na 2 SO 4 ). The solvent was evaporated under reduced pressure and the residual oil was purified by column chromatography on silica gel eluting with the appropriate mixture of EtOAc:petroleum ether (40-60° C.).
U. The cyanhydrine (1 mmol) was treated with 6N HCl (10 mL) in MeOH for 18 h at room temperature. The organic solvent was evaporated and a saturated aqueous solution of K 2 CO 3 was added to pH neutralization. After extraction with CH 2 Cl 2 (3×15 mL), the combined organic phases were washed with brine and dried (Na 2 SO 4 ). The solvent was evaporated under reduced pressure and the residual oil was purified by column chromatography on silica gel eluting with the appropriate mixture of EtOAc:petroleum ether (40-60° C.).
V. To a stirred solution of the Z-protected amino compound (1 mmol) in MeOH (8 mL) were added successively a catalytic amount of 10% Pd/C and anhydrous ammonium formate (5 mmol). After stirring for 2 h at rt, the reaction mixture was filtered over celite. The organic layer was then concentrated under reduced pressure to yield the crude product, which was used without any further purification.
W. To a stirred solution of phenylacetic acid (1.0 mmol) and the amino component (1.0 mmol) in dry CH 2 Cl 2 (10 mL), Et 3 N (1.1 mmol) and subsequently 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide (WSCI) (1.1 mmol) and 1-hydroxybenzotriazole (HOBt) (1.0 mmol) were added at 0° C. The reaction mixture was stirred for 1 h at 0° C. and overnight at rt. The solvent was evaporated under reduced pressure and EtOAc (20 mL) was added. The organic layer was washed consecutively with brine, 1N HCl, brine, 5% NaHCO 3 , and brine, dried over Na 2 SO 4 and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel eluting with the appropriate mixture of EtOAc:petroleum ether (40-60° C.).
X. A solution of the text-butyl ester derivative (1 mmol) in 50% TFA/CH 2 Cl 2 (10 mL) was stirred for 1 h at room temperature. The organic solvent was evaporated under reduced pressure to afford the desired product.
[0176] Compounds 1-3
[0000]
Characterising Data
1-(Thiazol-2-yl)hexadecan-1-ol (2a)
[0177] Procedure A
[0000]
[0178] White solid. Yield 51%.
[0179] m.p. 69-71° C.
[0180] 1 H NMR: δ 7.68 (d, 1H, J=2.8 Hz, ArH), 7.25 (d, 1H, J=2.8 Hz, ArH), 4.97 (m, 1H, CHOH), 3.14 (br s, 1H, OH), 1.86 (m, 2H, CH 2 CHOH), 1.48-1.13 (m, 26H, 13×CH 2 ), 0.86 (t, 3H, J=6.2 Hz, CH 3 ).
[0181] 13 C NMR: δ 175.6, 142.0, 118.8, 71.8, 38.3, 31.9, 29.7, 29.6, 29.6, 29.5, 29.4, 29.3, 25.2, 22.7, 14.1.
5-Phenyl-1-(thiazol-2-yl)pentan-1-ol (2b)
[0182] Procedure A
[0000]
[0183] Colorless Oil. Yield 42%.
[0184] 1 H NMR: δ 7.65 (d, 1H, J=3.4 Hz, ArH), 7.33-7.16 (m, 6H, Ph, ArH), 4.97 (m, 1H, CHOH), 4.5 (br, 1H, OH), 2.62 (t, 2H, J=7.0 Hz, CH 2 Ph), 2.05-1.80 (m, 2H, CH 2 CHOH), 1.74-1.45 (m, 4H, 2×CH 2 ).
[0185] 13 C NMR: δ 176.3, 142.3, 141.8, 128.3, 128.2, 125.6, 118.7, 71.4, 37.9, 35.7, 31.1, 24.9.
(Z)-1-(Thiazol-2-yl)octadec-9-en-1-ol (2c)
[0186] Procedure A
[0000]
[0187] C 21 H 37 NOS
[0188] White oil.
[0189] 1 H NMR (CDCl 3 ) δ: 7.69 (d, 1H, J=3.4 Hz, CHN), 7.28 (d, 1H, J=3.4 Hz, CHS), 5.34 (m, 2H, CH═CH), 4.97 (dd, 1H, J 1 =7.4 Hz, J 2 =5.2 Hz, CHOH), 3.47 (b, 1H, OH), 2.00 (m, 6H, 3×CH 2 ), 1.60-1.10 (m, 22H, 11×CH 2 ), 0.88 (t, 3H, J=6.2 Hz, CH 3 ).
[0190] 13 C NMR (CDCl 3 ) δ: 175.7, 142.0, 129.9, 129.8, 118.7, 71.8, 38.3, 31.9, 29.7, 29.5, 29.3, 29.2, 27.1, 25.2, 22.6, 14.1.
(5Z,8Z,11Z,14Z)-1-(Thiazol-2-yl)icosa-5,8,11,14-tetraen-1-ol (2d)
[0191] Procedure A
[0000]
[0192] C 23 H 35 NOS
[0193] MW: 373.60.
[0194] White oil.
[0195] 1 H NMR (CDCl 3 ) (δ: 7.64 (d, 1H, J=3.0 Hz, ArH), 7.23 (d, 1H, J=3.0 Hz, ArH), 5.56-5.21 (m, 8H, 4×CH═CH), 4.96 (dd, 1H, J 1 =6.8 Hz, J 2 =5.0 Hz, CHOH), 4.20-3.90 (br, 1H, OH), 2.98-2.63 (m, 6H, 3×CHCH 2 CH), 2.18-1.79 (m, 6H, 3×CH 2 ), 1.69-1.18 (m, 8H, 4×CH 2 ), 0.90 (t, 3H, J=6.6 Hz, CH 3 ).
[0196] 13 C NMR (CDCl 3 ) δ: 175.8, 141.9, 130.4, 129.5, 128.5, 128.2, 128.0, 127.9, 127.8, 127.5, 118.7, 71.5, 37.7, 31.4, 29.2, 27.1, 26.8, 25.5, 25.4, 25.1, 22.5, 14.0.
[0197] MS (ESI) m/z (%): 373 [M + , 100].
1-(Thiazol-2-yl)hexadecan-1-one (3a)
[0198] Procedure B
[0000]
[0199] C 19 H 33 NOS
[0200] MW: 323.54.
[0201] White solid.
[0202] m.p.: 39-41° C.
[0203] 1 H NMR (200 MHz, CDCl 3 ) δ=7.98 (d, 1H, J=3.0 Hz, ArH), 7.65 (d, 1H, J=3.0 Hz, ArH), 3.14 (t, 2H, J=7.4 Hz, CH 2 CO), 1.81-1.68 (m, 2H, CH 2 CH 2 CO), 1.42-1.10 (m, 24H, 12×CH 2 ), 0.86 (t, 3H, J=5.0 Hz, CH 3 ).
[0204] 13 C NMR (50 MHz, CDCl 3 ) δ=194.1, 167.3, 144.6, 126.0, 38.5, 31.9, 29.6, 29.4, 29.3, 29.2, 24.0, 22.7, 14.1.
[0205] MS (ESI) m/z (%): 324 [M+H, 100] + .
5-Phenyl-1-(thiazol-2-yl)pentan-1-one (3b)
[0206] Procedure B
[0000]
[0207] C 14 H 15 NOS
[0208] MW: 245.34.
[0209] Yellow oil.
[0210] 1 H NMR (200 MHz, CDCl 3 ) δ=8.00 (d, 1H, J=3.0 Hz, ArH), 7.66 (d, 1H, J=2.8 Hz, ArH), 7.33-7.13 (m, 5H, Ph), 3.21 (t, 2H, J=6.6 Hz, CH 2 CO), 2.68 (t, 2H, J=7.6 Hz, PhCH 2 ), 1.92-1.65 (m, 4H, 2×CH 2 ).
[0211] 13 C NMR (50 MHz, CDCl 3 ) δ=193.8, 167.1, 144.5, 142.0, 128.3, 128.2, 126.1, 125.6, 38.2, 35.6, 30.9, 23.6.
(Z)-1-(Thiazol-2-yl)octadec-9-en-1-one (3c)
[0212] Procedure B
[0000]
[0213] C 21 H 35 NOS
[0214] Yellowish oil.
[0215] 1 H NMR (CDCl 3 ) δ: 8.00 (d, 1H, J=3.0 Hz, CHN), 7.66 (d, 1H, J=3.0 Hz, CHS), 5.34 (m, 2H, CH═CH), 3.16 (t, 2H, J=8.0 Hz, CH 2 CO), 2.01 (m, 4H, 2×CH 2 CH═), 1.80-1.60 (m, 2H, CH 2 ), 1.60-1.10 (m, 20H, 10×CH 2 ), 0.88 (t, 3H, J=6.2 Hz, CH 3 ). 13 C NMR (CDCl 3 ) δ: 194.1, 167.4, 144.6, 130.0, 129.7, 126.0, 38.5, 32.6, 31.9, 29.7, 29.5, 29.3, 29.2, 29.1, 27.2, 24.0, 22.7, 14.1.
(5Z,8Z,11Z,14Z)-1-(Thiazol-2-yl)icosa-5,8,11,14-tetraen-1-one (3d)
[0216] Procedure B
[0000]
[0217] C 23 H 33 NOS
[0218] Yellowish oil.
[0219] 1 H NMR (CDCl 3 ) δ: 8.00 (d, 1H, J=2.8 Hz, ArH), 7.66 (d, 1H, J=2.8 Hz, ArH), 5.42-5.21 (m, 8H, 4×CH═CH), 3.19 (t, 2H, J=7.2 Hz, CH 2 CO), 2.88-2.63 (m, 6H, 3×CHCH 2 CH), 2.25-2.20 (m, 4H, 2×CH 2 ), 1.45-1.17 (m, 2H, CH 2 ), 1.40-1.20 (m, 6H, 3×CH 2 ), 0.88 (t, 3H, J=6.4 Hz, CH 3 ).
[0220] 13 C NMR (CDCl 3 ) δ: 193.9, 167.2, 144.6, 130.4, 129.1, 128.9, 128.5, 128.2, 128.1, 127.9, 127.5, 126.1, 37.8, 31.5, 29.3, 29.2, 27.2, 26.6, 25.6, 23.9, 22.5, 14.0.
[0221] Compounds 3 to 5 (Alternative Strategies)
[0000]
N-Methoxy-N-methyl-palmitamide (4a)
[0222] Procedure C
[0000]
[0223] C 18 H 37 NO 2
[0224] MW: 299.49.
[0225] colorless oil. Yield 81%.
[0226] 1 H NMR (200 MHz, CDCl 3 ) δ=3.66 (s, 3H, OMe), 3.16 (s, 3H, NMe), 2.39 (t, 2H, J=7.6 Hz, CH 2 CO), 1.70-1.57 (m, 2H, CH 2 CH 2 CO), 1.23-1.08 (m, 24H, 12×CH 2 ), 0.86 (t, 3H, J=3.8 Hz, CH 3 ).
[0227] 13 C NMR (50 MHz, CDCl 3 ) δ=174.6, 61.0, 31.8, 29.5, 29.4, 29.3, 24.8, 24.5, 22.5, 13.9.
[0228] MS (ESI) m/z (%): 300 [M+H, 100] + .
N-Methoxy-N-methyl-5-phenylpentanamide (4b) (by the Weinreb method)
[0229] Procedure C
[0000]
[0230] C 13 H 19 NO 2
[0231] MW: 221.30.
[0232] Colorless oil. Yield 81%.
[0233] 1 H NMR (200 MHz, CDCl 3 ) δ=7.33-7.12 (m, 5H, Ph), 3.65 (s, 3H, OMe), 3.17 (s, 3H, NMe), 2.65 (t, 2H, J=7.2 Hz, PhCH 2 ), 2.44 (t, 2H, J=7.2 Hz, CH 2 CO), 1.72-1.66 (m, 4H, 2×CH 2 ).
[0234] 13 C NMR (50 MHz, CDCl 3 ) δ=174.6, 142.2, 128.2, 128.1, 125.6, 61.0, 35.6, 31.6, 31.1, 24.2.
[0235] MS (ESI) m/z (%): 222 [M+H, 100] + .
General Procedure for the Synthesis of Morpholine Amides
[0236] To a stirred solution of acid (1 eq.) in dry CH 2 Cl 2 (7 mL), DMF (0.5 eq.) was added followed by oxalyl chloride (3 eq.) at room temperature. The reaction mixture was left stirring for 3 h. The solvent was removed and dry Et 2 O (7 mL) was added and cooled at 0° C. Pyridine (5 eq.) was added drop-wise, followed by drop-wise adittion of morpholine (5 eq.). The reaction mixture was left stirring for 18 h at room temperature. Then, H 2 O (8 mL) was added and it was left stirring for 30 min. The layers were separated and the organic layer was washed with an aqueous solution of HCl 1N (3×10 mL), brine (1×10 mL), an aqueous solution of NaHCO 3 5% (3×10 mL) and brine (1×10 mL). The organic layer was dried (Na 2 SO 4 ) and concentrated under reduced pressure. Purification by flash chromatography eluting with the appropriate mixture of EtOAc:pet. ether (40-60° C.) afforded the desired product.
1-Morpholinohexadecan-1-one (5a)
[0237] Procedure D
[0000]
[0238] C 20 H 39 NO 2
[0239] MW: 325.53.
[0240] White solid. Yield 99%.
[0241] m.p.: 45-46° C.
[0242] 1 H NMR (200 MHz, CDCl 3 ) δ=3.66-3.60 (m, 6H, CH 2 OCH 2 , CHHNCHH), 3.43-3.38 (m, 2H, CHHNCHH), 2.28 (t, 2H, J=7.2 Hz, CH 2 CO), 1.63-1.52 (m, 2H, CH 2 CH 2 CO), 1.34-1.06 (m, 24H, 12×CH 2 ), 0.85 (t, 3H, J=5.8 Hz, CH 3 ).
[0243] 13 C NMR (50 MHz, CDCl 3 ) δ=171.8, 66.8, 66.6, 45.9, 41.7, 33.0, 31.8, 29.6, 29.5, 29.4, 29.3, 29.2, 25.2, 22.6, 14.0.
[0244] MS (ESI) m/z (%): 326 [M+H, 100] + .
1-Morpholino-5-phenylpentan-1-one (5b)
[0245] Procedure D
[0000]
[0246] C 15 H 21 NO 2
[0247] MW: 247.33.
[0248] Colorless oil. Yield 74% (1.025 g).
[0249] 1 H NMR (200 MHz, CDCl 3 ) δ=7.26-7.09 (m, 5H, Ph), 3.64-3.42 (m, 6H, CH 2 OCH 2 , CHHNCHH), 3.41-3.23 (m, 2H, CHHNCHH), 2.61 (t, 2H, J=7.0 Hz, PhCH 2 ), 2.27 (t, 2H, J=7.2 Hz, CH 2 CO), 1.69-1.60 (m, 411, 2×CH 2 ).
[0250] 13 C NMR (50 MHz, CDCl 3 ) δ=171.3, 141.9, 128.2, 128.1, 125.5, 66.7, 66.4, 45.7, 41.6, 35.5, 32.7, 30.9, 24.6.
[0251] MS (ESI) m/z (%): 248 [M+H, 100] + , 270 [M+23, 23].
Synthesis of 2-Oxo-Thiazoles Using the Weinreb and Morpholino Amide Method
[0252] To a stirred solution of thiazole (3 eq.) in dry Et 2 O (20 mL) at −78° C. under a dry argon atmosphere was added a solution of n-BuLi (1.6 M in hexanes, 3 eq.) drop-wise over a period of 10 min. The resulting orange solution was stirred for 45 min. Then a solution of the amide (1 eq.) in dry Et 2 O (2 mL) was slowly added giving the mixture a dark brown color. After stirring for 30 min. at −78° C., the mixture was allowed to warm up to room temperature over a period of 2 h. Then, saturated aqueous ammonium chloride solution was added and the mixture was extracted with ether (2×10 mL). The combined extracts were washed with brine and then dried over Na 2 SO 4 and concentrated under reduced pressure. Purification by flash chromatography eluting with the appropriate mixture of EtOAc:pet. ether (40-60° C.) afforded the desired product.
1-(Thiazol-2-yl)hexadecan-1-one (3a)
[0253] Procedure E
[0254] Yield when the Weinreb amide was used: 73%.
[0255] Yield when the morpholine amide was used: 98%.
5-Phenyl-1-(thiazol-2-yl)pentan-1-one (3b)
[0256] Procedure E
[0257] Yield when the Weinreb amide was used: 85%.
[0258] Yield when the morpholine amide was used: 86%.
[0259] Compounds 6 to 9
[0000]
3-(4-(Hexyloxy)phenyl)propanal (7)
[0260] Procedure F then G
[0000]
[0261] C 15 H 22 O 2
[0262] MW: 234.33
[0263] Orange oil. Yield 64%.
[0264] 1 H NMR (200 MHz, CDCl 3 ) δ=9.80 (s, 1H, CHO), 7.09 (d, 2H, J=8.4 Hz, CH), 6.82 (d, 2H, J=8.6 Hz, 2×CH), 3.92 (t, 2H, J=6.4 Hz, CH 2 ), 3.00-2.85 (m, 2H, CH 2 ), 2.80-2.65 (m, 2H, CH 2 ), 1.85-1.65 (m, 2H, CH 2 ), 1.50-1.20 (m, 6H, 3×CH 2 ), 0.92 (m, 3H, CH 3 ).
[0265] 13 C NMR (50 MHz, CDCl 3 ) δ=201.7, 157.6, 132.0, 129.1, 114.5, 67.9, 45.5, 31.5, 29.2, 27.2, 25.7, 22.5, 14.0
3-(4-(Hexyloxy)phenyl)-1-(thiazol-2-yl)propan-1-ol (8)
[0266] Procedure A
[0000]
[0267] C 18 H 25 NO 2 S
[0268] MW: 319.46
[0269] Colorless oil. Yield 66%.
[0270] 1 H NMR (200 MHz, CDCl 3 ) δ=7.65 (d, 1H, J=3.2 Hz, ArH), 7.24 (d, 1H, J=3.4 Hz, ArH), 7.07 (d, 2H, J=8.8 Hz, 2×CH), 6.79 (d, 2H, J=8.6 Hz, 2×CH), 4.96 (dd, 1H, J, =7.6 Hz, J 2 =5.0 Hz, CH), 3.90 (t, 2H, J=6.4 Hz, CH 2 O), 2.80-2.60 (m, 2H, CH 2 ), 2.25-2.05 (m, 2H, CH 2 ), 1.85-1.65 (m, 2H, CH 2 ), 1.50-1.30 (m, 6H, 3×CH 2 ), 0.88 (t, 3H, J=6.2 Hz, CH 3 ).
[0271] 13 C NMR (50 MHz, CDCl 3 ) δ=175.9, 157.4, 142.0, 133.0, 129.3, 118.8, 114.4, 70.9, 67.9, 39.9, 31.5, 30.5, 29.2, 25.6, 22.5, 14.0.
3-(4-(Hexyloxy)phenyl)-1-(thiazol-2-yl)propan-1-one (9)
[0272] Procedure B
[0000]
[0273] C 18 H 23 NO 2 S
[0274] MW: 317.45
[0275] Yellowish oil. Yield 78%.
[0276] 1 H NMR (200 MHz, CDCl 3 ) δ=7.95 (d, 1H, J=3.2 Hz, ArH), 7.62 (d, 1H, J=3.4 Hz, ArH), 7.15 (d, 2H, J=8.8 Hz, CH), 6.81 (d, 2H, J=8.4 Hz, CH), 3.90 (t, 2H, J=6.6 Hz, CH 2 O), 3.45 (t, 2H, J=7.2 Hz, CH 2 ), 3.01 (t, 2H, J=3.8 Hz, CH 2 ), 1.90-1.64 (m, 2H, CH 2 ), 1.58-1.20 (m, 6H, 3×CH 2 ), 0.89 (t, 3H, J=6.6 Hz, CH 3 ).
[0277] 13 C NMR (50 MHz, CDCl 3 ) δ=193.1, 167.1, 157.5, 144.6, 132.5, 129.3, 126.1, 114.5, 68.0, 40.3, 31.5, 29.2, 28.9, 25.7, 22.6, 14.0.
[0278] MS (ESI) m/z (%): 318 [M+H, 100] + .
[0279] Compounds 10 to 15
[0000]
2-(tert-Butyldimethylsilyloxy)heptadecanenitrile (11a)
[0280] Procedure H
[0000]
[0281] C 23 H 47 NOSi
[0282] MW: 381.71
[0283] Colorless oil. Yield 85%.
[0284] 1 H NMR (200 MHz, CDCl 3 ) δ=4.41 (t, 1H, J=6.4 Hz, CH), 1.70-1.90 (m, 2H, CH 2 ), 1.40-1.55 (m, 2H, CH 2 ), 1.30-1.15 (m, 24H, 12×CH 2 ), 1.03-0.82 (m, 12H, 4×CH 3 ), 0.19 (s, 3H, CH 3 ), 0.14 (s, 3H, CH 3 ).
[0285] 13 C NMR (50 MHz, CDCl 3 ) δ=120.1, 61.9, 36.3, 31.9, 29.6, 29.5, 29.4, 29.3, 28.9, 25.5, 24.5, 22.7, 18.0, 14.1, −5.2, −5.4.
2-(tert-Butyldimethylsilyloxy)-6-phenylhexanenitrile (11b)
[0286] Procedure H
[0000]
[0287] C 18 H 29 NOSi
[0288] MW: 303.51 Colorless oil. Yield 82%.
[0289] 1 H NMR (CDCl 3 ): δ=7.34-7.20 (m, 5H, Ph), 4.44 (t, 1H, J=6.6 Hz, CH), 2.68 (t, 2H, J=7.4 Hz, CH 2 ), 1.88-1.80 (m, 2H, CH 2 ), 1.76-1.69 (m, 2H, CH 2 ), 1.68-1.58 (m, 2H, CH 2 ), 0.97 (s, 9H, 3×CH 3 ), 0.23 (s, 3H, CH 3 ), 0.18 (s, 3H, CH 3 ).
[0290] 13 C NMR (CDCl 3 ) δ=142.0, 128.3, 128.0, 125.8, 120.1, 61.8, 36.1, 35.6, 30.8, 25.7, 25.5, 24.1, 18.0, −5.2, −5.4.
2-(tert-Butyldimethylsilyloxy)heptadecanamide (12a)
[0291] Procedure I
[0000]
[0292] C 23 H 49 NO 2 Si
[0293] MW: 399.73
[0294] Yellow oil. Yield 63%.
[0295] 1 H NMR (200 MHz, CDCl 3 ) δ=6.49 (s, 1H, NHH), 6.14 (s, 1H, NHH), 4.10 (t, 1H, J=5.0 Hz, CH), 1.80-1.56 (m, 2H, CH 2 ), 1.40-1.10 (m, 26H, 13×CH 2 ), 0.95-0.80 (m, 12H, 4×CH 3 ), 0.17 (s, 3H, CH 3 ), 0.14 (s, 3H, CH 3 ).
[0296] 13 C NMR (50 MHz, CDCl3) δ 177.3, 73.4, 35.1, 31.9, 29.7, 29.6, 29.5, 29.4, 29.3, 25.7, 24.1, 22.7, 18.0, 14.1, −4.9, −5.3.
[0297] MS (ESI) m/z (%) δ=400 [M+H, 40] + , 422 [M+Na, 100] + .
2-(tert-Butyldimethylsilyloxy)-6-phenylhexanamide (12b)
[0298] Procedure I
[0000]
[0299] C 18 H 31 NO 2 Si
[0300] MW: 321.53
[0301] Colorless oil. Yield 100%.
[0302] 1 H NMR (CDCl 3 ): δ=7.28-7.15 (m, 5H, Ph), 6.51 (s, 1H, NH), 5.61 (s, 1H, NH), 4.16 (t, 1H, J=6.6 Hz, CH), 2.62 (t, 2H, J=7.4 Hz, CH 2 ), 1.77-1.32 (m, 6H, 3×CH 2 ), 0.91 (s, 9H, 3×CH 3 ), 0.06 (s, 6H, 2×CH 3 ).
[0303] 13 C NMR (CDCl 3 ): δ=177.4, 142.3, 128.2, 128.1, 125.5, 73.2, 35.6, 34.8, 31.2, 25.6, 23.8, 17.8, −5.0, −5.4.
[0304] MS (ESI) m/z (%): 322 [M+H, 100] + .
2-(tert-Butyldimethylsilyloxy)heptadecanethioamide (13a)
[0305] Procedure J
[0000]
[0306] C 23 H 49 NOSSi
[0307] MW: 415.79
[0308] Yellowish oil. Yield 84%.
[0309] 1 H NMR (200 MHz, CDCl 3 ) δ=7.96 (s, 1H, NHH), 7.74 (s, 1H, NM), 4.56 (t, 1H, J=5.0 Hz, CH), 1.90-1.70 (m, 2H, CH 2 ), 1.47-1.15 (m, 26H, 13×CH 2 ), 1.00-0.83 (m, 12H, 4×CH 3 ), 0.12 (s, 3H, CH 3 ), 0.09 (s, 3H, CH 3 ).
[0310] 13 C NMR (50 MHz, CDCl3) δ=210.3, 80.1, 38.0, 32.1, 29.9, 29.8, 29.7, 29.6, 26.0, 25.7, 24.1, 22.9, 18.3, 14.3, −4.7, −4.9.
[0311] MS (ESI) m/z (%): 416 [M+H, 90] + .
2-(tert-Butyldimethylsilyloxy)-6-phenylhexanethioamide (13b)
[0312] Procedure J
[0000]
[0313] C 18 H 31 NOSSi
[0314] MW: 337.60
[0315] Yellowish oil. Yield 64%.
[0316] 1 H NMR (CDCl 3 ): δ=8.28 (s, 1H, NH), 7.98 (s, 1H, NH), 7.24-7.10 (m, 5H, Ph), 4.52 (t, 1H, J=6.6 Hz, CH), 2.57 (t, 2H, J=7.4 Hz, CH 2 ), 1.95-1.80 (m, 2H, CH 2 ), 1.62-1.45 (m, 2H, CH 2 ), 1.42-1.25 (m, 2H, CH 2 ), 0.88 (s, 9H, 3×CH 3 ), 0.06 (s, 3H, SiCH 3 ), 0.04 (s, 3H, SiCH 3 ).
[0317] 13 C NMR (CDCl 3 ): 209.6, 142.3, 128.3, 128.1, 125.5, 79.6, 37.4, 35.6, 31.2, 25.6, 23.5, 17.9, −5.1, −5.3.
[0318] MS (ESI) m/z (%): 338 [M+H, 100] + .
Ethyl 2-(1-hydroxyhexadecyl)thiazole-4-carboxylate (14a)
[0319] Procedure K
[0000]
[0320] C 22 H 39 NO 3 S
[0321] MW: 397.61
[0322] Yellowish solid. Yield 74%.
[0323] 1 H NMR (200 MHz, CDCl 3 ) δ=8.06 (s, 1H, CH), 5.03 (dd, 1H, J, =4.5 Hz, J 2 =8.1 Hz, CH), 4.36 (q, 2H, J=7.1 Hz, CH 2 ), 3.10-2.90 (br, 1H, OH), 2.00-1.60 (m, 2H, CH 2 ), 1.35 (t, 3H, J=7.1 Hz, CH 3 ), 1.40-1.10 (m, 26H, 13×CH 2 ), 0.85 (t, 3H, J=6.8 Hz, CH 3 ).
[0324] 13 C NMR (50 MHz, CDCl 3 ) δ=177.3, 161.4, 146.6, 127.1, 71.8, 61.3, 38.1, 31.8, 29.6, 29.5, 29.4, 29.3, 29.2, 25.5, 25.1, 22.6, 14.2, 14.0.
Ethyl 2-(1-hydroxy-5-phenylpentyl)thiazole-4-carboxylate (14b)
[0325] Procedure K
[0000]
[0326] C 17 H 21 NO 3 S
[0327] MW: 319.42
[0328] Yellowish oil. Yield 45%.
[0329] 1 H NMR (CDCl 3 ): δ=8.03 (s, 1H, ArH), 7.25-7.10 (m, 5H, Ph), 5.11-5.00 (m, 1H, CH), 4.33 (q, 2H, J=5.8 Hz, OCH 2 ), 4.10-3.95 (m, 1H, OH), 2.56 (t, 2H, J=7.0 Hz, CH 2 ), 1.85-1.78 (m, 2H, CH 2 ), 1.62-1.41 (m, 2H, CH 2 ), 1.32 (t, 3H, J=5.8 Hz, CH 3 ), 1.24-1.20 (m, 2H, CH 2 ).
[0330] 13 C NMR (CDCl 3 ): δ=177.4, 161.3, 146.4, 142.2, 128.2, 128.1, 127.2, 125.5, 71.5, 61.3, 37.8, 35.5, 30.9, 24.7, 14.2.
Ethyl 2-palmitoylthiazole-4-carboxylate (15a)
[0331] Procedure B
[0000]
[0332] C 22 H 37 NO 3 S
[0333] MW: 395.60
[0334] White solid. Yield 82%.
[0335] 1 H NMR (200 MHz, CDCl 3 ): δ=8.41 (s, 1H, CH), 4.46 (q, 2H, J=6.8 Hz, CH 2 ), 3.23 (t, 2H, J=7.4 Hz, CH 2 ), 1.85-1.60 (m, 4H, 2×CH 2 ), 1.43 (t, 3H, J=6.8 Hz, CH 3 ), 1.42-1.00 (m, 22H, 11×CH 2 ), 0.88 (t, 3H, J=6.8 Hz, CH 3 ).
[0336] 13 C NMR (50 MHz, CDCl 3 ): δ=194.3, 167.9, 161.1, 148.9, 133.2, 62.0, 38.6, 32.1, 29.9, 29.8, 29.7, 29.6, 29.5, 29.3, 23.8, 22.9, 14.5, 14.3.
[0337] MS (ESI) m/z (%): 418 [M+Na, 100] + .
Ethyl 2-(5-phenylpentanoyl)thiazole-4-carboxylate (15b)
[0338] Procedure B
[0000]
[0339] C 17 H 19 NO 3 S
[0340] MW: 317.40
[0341] Yellowish oil. Yield 81%
[0342] 1 H NMR (CDCl 3 ): δ=8.38 (s, 1H, ArH), 7.24-7.13 (m, 5H, Ph), 4.42 (q, 2H, J=5.8 Hz, OCH 2 ), 3.23 (t, 2H, J=5.8 Hz, CH 2 ), 2.63 (t, 2H, J=7.0 Hz, CH 2 CO), 1.81-1.65 (m, 4H, 2×CH 2 ), 1.39 (t, 3H, J=5.8 Hz, CH 3 ).
[0343] 13 C NMR (CDCl 3 ): 193.8, 167.4, 160.8, 148.6, 142.0, 133.1, 128.3, 128.2, 125.7, 61.8, 38.1, 35.6, 30.7, 23.2, 14.3.
[0344] MS (ESI) m/z (%): 318 [M+H, 100] + .
[0345] Compounds 16 to 19
[0000]
5-(4-(Hexyloxy)phenyl)pentanal (17)
[0346] Procedure N then G
[0000]
[0347] C 17 H 26 O 2
[0348] MW: 262.39.
[0349] Yelloish oil. Yield 97%.
[0350] 1 H NMR (200 MHz, CDCl 3 ) δ=9.73 (t, 1H, J=1.8 Hz, CHO), 7.06 (d, 2H, J=8.6 Hz, CH, Ph), 6.81 (d, 2H, J=8.6 Hz, CH, Ph), 3.92 (t, 2H, J=6.4 Hz, CH 2 OPh), 2.56 (t, 2H, J=7.0 Hz, PhCH 2 ), 2.47-2.35 (m, 2H, CH 2 CHO), 1.81-1.67 (m, 2H, CH 2 CH 2 OPh), 1.65-1.57 (m, 4H, 2×CH 2 ), 1.55-1.09 (m, 6H, 3×CH 2 ), 0.90 (t, 3H, J=6.8 Hz, CH 3 ).
[0351] 13 C NMR (50 MHz, CDCl 3 ) δ=202.3, 157.2, 133.6, 129.0, 114.2, 67.8, 43.6, 34.6, 31.5, 31.0, 29.2, 25.6, 22.5, 21.5, 20.8, 13.9.
5-(4-(Hexyloxy)phenyl)-1-(thiazol-2-yl)pentan-1-ol (18)
[0352] Procedure A
[0000]
[0353] C 20 H 29 NO 2 S
[0354] MW: 347.51.
[0355] Orange oil. Yield 74%.
[0356] 1 H NMR (200 MHz, CDCl 3 ) δ=7.62 (d, 1H, J=3.2 Hz, ArH), 7.22 (d, 1H, J=3.4 Hz, ArH), 7.03 (d, 2H, J=8.8 Hz, CH, Ph), 6.77 (d, 2H, J=8.6 Hz, CH, Ph), 4.98-4.84 (m, 1H, CHOH), 4.46 (d, 1H, J=5 Hz, CHOH), 3.89 (t, 2H, J=6.4 Hz, CH 2 OPh), 2.52 (t, 2H, J=7 Hz, PhCH 2 ), 2.48-1.19 (m, 14H, 7×CH 2 ), 0.88 (t, 3H, J=6.6 Hz, CH 3 ).
[0357] 13 C NMR (50 MHz, CDCl 3 ) δ=176.3, 157.0, 141.9, 134.2, 129.0, 118.5, 114.1, 71.5, 67.8, 38.0, 34.7, 31.5, 31.3, 29.2, 25.6, 24.7, 22.5, 20.9, 14.0.
[0358] MS (ESI) m/z (%): 348 [M+H, 100] + .
5-(4-(Hexyloxy)phenyl)-1-(thiazol-2-yl)pentan-1-one (19)
[0359] Procedure G
[0000]
[0360] C 20 H 27 NO 2 S
[0361] MW: 345.50.
[0362] Yellowish oil. Yield 89%.
[0363] 1 H NMR (200 MHz, CDCl 3 ) δ=7.98 (d, 1H, J=3.2 Hz, ArH), 7.65 (d, 1H, J=3.4 Hz, ArH), 7.08 (d, 2H, J=8.8 Hz, CH, Ph), 6.81 (d, 2H, J=8.4 Hz, CH, Ph), 3.91 (t, 2H, J=6.6 Hz, CH 2 OPh), 3.18 (t, 2H, J=6.8 Hz, CH 2 CO), 2.60 (t, 2H, J=7.6 Hz, PhCH 2 ), 1.89-1.61 (m, 6H, 3×CH 2 ), 1.48-1.28 (m, 6H, 3×CH 2 ), 0.90 (t, 3H, J=6.6 Hz, CH 3 ).
[0364] 13 C NMR (50 MHz, CDCl 3 ) δ=193.7, 167.1, 157.2, 144.5, 133.9, 129.1, 126.1, 114.2, 67.8, 38.2, 34.6, 31.5, 31.1, 29.2, 25.6, 23.5, 22.5, 14.0.
[0365] MS (ESI) m/z (%): 346 [M+H, 100] +
[0366] Compounds 20 to 24
[0000]
[0367] (a) Br(CH 2 ) 3 COOC 2 H 5 , K 2 CO 3 , KI, acetone, reflux; (b) i. LiAlH 4 , dry Et 2 O, −20° C., ii. NaOCl, NaHCO 3 , NaBr, 4-AcNH-TEMPO, toluene, AcOEt, H 2 O, −5° C.; (c) thiazole, n-BuLi, dry Et 2 O, −78° C.; (d) NaOCl, NaHCO 3 , NaBr, 4-AcNH-TEMPO, toluene, AcOEt, H 2 O, −5° C.
Ethyl 4-(4-octylphenoxy)butanoate (21)
[0368] Procedure O
[0000]
[0369] C 20 H 32 O 3
[0370] MW: 320.47.
[0371] Colorless oil. Yield 100%.
[0372] 1 H NMR (200 MHz, CDCl 3 ) δ=7.08 (d, 2H, J=7.8 Hz, CH, Ph), 6.81 (d, 2H, J=7.6 Hz, CH, Ph), 4.15 (q, 2H, J=7.0 Hz, COOCH 2 ), 3.99 (t, 2H, J=5.8 Hz, PhOCH 2 ), 2.58-2.42 (m, 4H, 2×CH 2 ), 2.17-2.06 (m, 2H, CH 2 CH 2 COO), 1.57-1.45 (m, 2H, CH 2 CH 2 Ph), 1.27 (br, 13H, 5×CH 2 , CH 3 ), 0.89 (t, 3H, J=5.2 Hz, CH 3 ).
[0373] 13 C NMR (50 MHz, CDCl 3 ) δ=173.2, 156.8, 135.0, 129.1, 114.2, 66.6, 60.3, 35.0, 31.7, 30.8, 29.4, 29.2, 24.6, 22.6, 14.1, 14.0.
[0374] MS (ESI) m/z (%): 321 [M+H, 100] + .
4-(4-Octylphenoxy)butanal (22)
[0375] Procedure N then G
[0000]
[0376] C 18 H 28 O 2
[0377] MW: 276.41.
[0378] Colorless oil. Yield 97%.
[0379] 1 H NMR (200 MHz, CDCl 3 ) δ=9.84 (t, 1H, J=1.4 Hz, CHO), 7.09 (d, 2H, J=8.6 Hz, CH, Ph), 6.81 (d, 2H, J=8.8 Hz, CH, Ph), 3.99 (t, 2H, J=6.0 Hz, PhOCH 2 ), 2.70-2.52 (m, 4H, 2×CH 2 ), 1.63-1.52 (m, 2H, CH 2 CH 2 Ph), 1.31-1.24 (br, 10H, 5×CH 2 ), 0.90 (t, 3H, J=6.4 Hz, CH 3 ).
[0380] 13 C NMR (50 MHz, CDCl 3 ) δ=201.7, 156.6, 135.2, 129.2, 114.1, 66.6, 40.6, 35.0, 31.8, 31.7, 29.4, 29.2, 22.6, 22.0, 14.0.
4-(4-Octylphenoxy)-1-(thiazol-2-yl)butan-1-ol (23)
[0381] Procedure A
[0000]
[0382] C 21 H 31 NO 2 S
[0383] MW: 361.54.
[0384] Orange oil. Yield 73%.
[0385] 1 H NMR (200 MHz, CDCl 3 ) δ=7.72 (d, 1H, J=3.2 Hz, ArH), 7.29 (d, 1H, J=3.2 Hz, ArH), 7.08 (d, 2H, J=8.8 Hz, CH, Ph), 6.81 (d, 2H, J=8.6 Hz, CH, Ph), 5.11 (dd, 1H, J j =4.4 Hz, J 2 =7.6 Hz, CHOH), 4.00 (t, 2H, J=6.0 Hz, PhOCH 2 ), 3.92 (s, 1H, OH), 2.54 (t, 2H, J=7.2 Hz, CH 2 Ph), 2.32-1.90 (m, 4H, 2×CH 2 ), 1.67-1.48 (m, 2H, CH 2 CH 2 Ph), 1.30-1.23 (br, 10H, 5×CH 2 ), 0.88 (t, 3H, J=6.2 Hz, CH 3 ).
[0386] 13 C NMR (50 MHz, CDCl 3 ) δ=175.4, 156.6, 142.0, 135.3, 129.2, 118.9, 114.3, 71.5, 67.7, 35.1, 35.0, 31.9, 31.7, 29.5, 29.2, 25.2, 22.6, 14.1.
[0387] MS (ESI) m/z (%): 362 [M+H, 100] + .
4-(4-Octylphenoxy)-1-(thiazol-2-yl)butan-1-one (24)
[0388] Procedure G
[0000]
[0389] C 21 H 29 NO 2 S
[0390] MW: 359.53.
[0391] Yellowish oil. Yield 85%.
[0392] 1 H NMR (200 MHz, CDCl 3 ) δ=7.99 (d, 1H, J=3.0 Hz, ArH), 7.65 (d, 1H, J=3.0 Hz, ArH), 7.07 (d, 2H, J=8.6 Hz, CH, Ph), 6.80 (d, 2H, J=8.8 Hz, CH, Ph), 4.06 (t, 2H, J=6.2 Hz, PhOCH 2 ), 3.39 (t, 2H, J=7.2 Hz, CH 2 C═O), 2.54 (t, 2H, J=7.4 Hz, CH 2 Ph), 2.26 (quintet, 2H, J=6.2 Hz, CH 2 CH 2 C═O), 1.68-1.45 (m, 2H, CH 2 CH 2 Ph), 1.30-1.23 (br, 10H, 5×CH 2 ), 0.89 (t, 3H, J=6.2 Hz, CH 3 ).
[0393] 13 C NMR (50 MHz, CDCl 3 ) δ=193.2, 166.9, 156.7, 144.6, 135.0, 129.1, 126.0, 114.2, 66.7, 35.1, 35.0, 31.8, 31.7, 29.4, 29.2, 23.6, 22.6, 14.0.
[0394] MS (ESI) m/z (%): 360 [M+H, 100] + .
[0395] Compounds 25 to 29
[0000]
[0396] (a) DAST, dry CH 2 Cl 2 , −78° C.; (b) i. LiAlH 4 , dry Et 2 O, −20° C., ii. (COCl) 2 , dry Et 3 N, dry DMSO, dry CH 2 Cl 2 , −60° C.; (c) thiazole, n-BuLi, dry THF, −78° C.; (d) Dess-Martin periodinane, dry CH 2 Cl 2 .
Methyl 2-fluorohexadecanoate (26)
[0397] Procedure P
[0000]
[0398] C 17 H 33 FO 2
[0399] MW: 288.44.
[0400] White solid. Yield 78%.
[0401] m.p.: 36-38° C.
[0402] 1 H NMR (200 MHz, CDCl 3 ) δ=4.91 (dt, 1H, J H-H =6.0 Hz, J H-F =48.8 Hz, CHF), 3.80 (s, 3H, COOCH 3 ), 2.00-1.77 (m, 2H, CH 2 CHF), 1.49-1.18 (m, 24H, 12×CH 2 ), 0.88 (t, 3H, J=6.8 Hz, CH 3 ).
[0403] 13 C NMR (50 MHz, CDCl 3 ) δ=170.5 (d, J C-C-F =24 Hz, COO), 89.0 (d, J C-F =183 Hz, CF), 52.2, 32.3 (d, =21 Hz, CH 2 CHF), 31.9, 29.6, 29.5, 29.4, 29.3, 29.0, 24.4, 24.3, 22.7, 14.1. 19 F NMR (186 MHz, CDCl 3 ) δ=−192.5 (quintet, CHF).
2-Fluorohexadecanal (27)
[0404] Procedure N then Q
[0000]
[0405] C 16 H 31 FO
[0406] MW: 258.42.
[0407] White solid. Yield 86%.
[0408] m.p.: 68-71° C.
[0409] 1 H NMR (200 MHz, CDCl 3 ) δ=9.76 (d, 1H, J=5.8 Hz, CHO), 4.74 (dt, 1H, J H-H =4.8 Hz, J H-F =49.0 Hz, CHF), 1.86-1.68 (m, 2H, CH 2 CHF), 1.47-1.10 (m, 24H, 12×CH 2 ), 0.88 (t, 3H, J=5.8 Hz, CH 3 ).
[0410] 13 C NMR (50 MHz, CDCl 3 ) δ=200.4 (d, J C-C-F =36 Hz, CO), 95.0 (d, J C-F =178 Hz, CF), 31.9, 30.3 (d, =20 Hz, CH 2 ), 29.6, 29.5, 29.3, 29.2, 24.2, 24.1, 22.7, 14.1.
[0411] 19 F NMR (186 MHz, CDCl 3 ) δ=−200.0 (m, CHF).
2-Fluoro-1-(thiazole-2-yl)hexadeca-1-ol (28)
[0412] Procedure A
[0000]
[0413] C 19 H 34 FNOS
[0414] MW: 343.54.
[0415] Yellowish solid. Yield 40%.
[0416] m.p.: 46-49° C.
[0417] 1 H NMR (200 MHz, CDCl 3 ) δ=7.89 (d, 1/7H, J=3.2 Hz, ArH), 7.75 (d, 6/7H, J=3.4 Hz, ArH), 7.45 (d, 1/7H, J=3.2 Hz, ArH), 7.35 (d, 6/7H, J=3.2 Hz, ArH), 5.22-5.05 (dm, 1H, J=13.4 Hz, CHOH), 5.01-4.66 (dm, 1H, J=51.6 Hz, CHF), 4.15 (d, ⅔H, J=4.6 Hz, CHOH), 3.91 (d, ⅓H, J=5.6 Hz, CHOH), 1.94-1.08 (m, 26H, 13×CH 2 ), 0.88 (t, 3H, J=6.2 Hz, CH 3 ).
[0418] 13 C NMR (50 MHz, CDCl 3 ) δ=170.0, 142.1, 119.7, 95.4 (d, J C-F =173 Hz, CF), 73.2 (d, J C-C-F =22 Hz, ⅓COH), 73.0 (d, J C-C-F =24 Hz, ⅔COH) 31.9, 30.6 (d, J C-C-F =21 Hz, CH 2 ), 29.6, 29.5, 29.4, 29.3, 25.0, 24.9, 22.7, 14.1.
[0419] 19 F NMR (186 MHz, CDCl 3 ) δ=−190.2 (m, CHF), −194.3 (m, CHF).
[0420] MS (ESI) m/z (%): 344 [M+H, 100] + .
2-Fluoro-1-(thiazole-2-yl)hexadeca-1-one (29)
[0421] Procedure B
[0000]
[0422] C 19 H 32 FNOS
[0423] MW: 341.53.
[0424] White solid. Yield 60%.
[0425] m.p.: 55-56° C.
[0426] 1 H NMR (200 MHz, CDCl 3 ) δ=8.05 (d, 1H, J=3.0 Hz, ArH), 7.76 (d, 1H, J=3.0 Hz, ArH), 6.07 (ddd, 1H, J H-F =49.8 Hz, J H-H =3.8 Hz, J H-H =8.2 Hz, CHF), 2.19-1.91 (m, 2H, CH 2 CHF), 1.66-1.08 (m, 24H, 12×CH 2 ), 0.87 (t, 3H, J=6.6 Hz, CH 3 ).
[0427] 13 C NMR (50 MHz, CDCl 3 ) δ=189.4 (d, J C-C-F =19 Hz, CO), 164.1, 145.3, 127.1, 92.9 (d, J C-F =182 Hz, CF), 32.8 (d, J C-C-F =21 Hz, CH 2 ), 32.1, 29.9, 29.8, 29.7, 29.6, 29.5, 29.3, 24.9, 22.9, 14.3. 19 F NMR (186 MHz, CDCl 3 ) δ=−196.6 (m, CHF).
[0428] MS (ESI) m/z (%): 342 [M+H, 100] + .
[0429] Compounds 30 to
[0000]
[0430] The following target compounds of the invention are synthesised according to the protocols above:
2-(4-(Hexyloxy)phenyl)ethanol (31)
[0431] Procedure O
[0000]
[0432] C 14 H 22 O 2
[0433] MW: 222.32.
[0434] Colorless oil. Yield 97%.
[0435] 1 H NMR (200 MHz, CDCl 3 ) δ=7.14 (d, 2H, J=8.6 Hz, CH, Ph), 6.85 (d, 2H, J=8.8 Hz, CH, Ph), 3.94 (t, 2H, J=6.4 Hz, CH 2 OPh), 3.82 (t, 2H, J=5.2 Hz, CH 2 OH), 2.81 (t, 2H, J=6.4 Hz, PhCH 2 ), 1.81-1.71 (m, 2H, CH 2 CH 2 OPh), 1.50-1.26 (m, 6H, 3×CH 2 ), 0.91 (t, 3H, J=6.8 Hz, CH 3 ).
[0436] 13 C NMR (50 MHz, CDCl 3 ) δ=157.8, 130.2, 129.8, 114.6, 68.0, 63.7, 38.2, 31.5, 29.2, 25.6, 22.5, 14.0.
2-(4-(Hexyloxy)phenyl)acetaldehyde (32)
[0437] Procedure G
[0000]
[0438] C 14 H 20 O 2
[0439] MW: 220.31.
[0440] Yellow oil. Yield 97%.
[0441] 1 H NMR (200 MHz, CDCl 3 ) δ=9.72 (t, 1H, J=2.4 Hz, CHO), 7.13 (d, 2H, J=8.4 Hz, CH, Ph), 6.90 (d, 2H, J=8.6 Hz, CH, Ph), 3.96 (t, 2H, J=6.4 Hz, CH 2 OPh), 3.63 (d, 2H, J=2.4 Hz, PhCH 2 ), 1.92-1.74 (m, 2H, CH 2 CH 2 OPh), 1.54-1.27 (m, 6H, 3×CH 2 ), 0.92 (t, 3H, J=6.8 Hz, CH 3 ).
[0442] 13 C NMR (50 MHz, CDCl 3 ) δ=199.4, 158.2, 130.3, 123.1, 114.7, 67.7, 49.4, 31.2, 28.9, 25.4, 22.3, 13.7.
(E)-Methyl 4-(4-(hexyloxy)phenyl)but-2-enoate (33)
[0443] Procedure R
[0000]
[0444] C 17 H 24 O 3
[0445] MW: 276.37.
[0446] Yellowish oil. Yield 86%.
[0447] 1 H NMR (200 MHz, CDCl 3 ) δ=7.16-7.05 (m, 3H, CH 2 CHCH, CH, Ph), 6.84 (d, 2H, J=8.0 Hz, CH, Ph), 5.79 (d, 1H, J=15.6 Hz, CHCOOMe), 3.94 (t, 2H, J=6.4 Hz, CH 2 OPh), 3.72 (s, 3H, COOCH 3 ), 3.46 (d, 2H, J=6.4 Hz, PhCH 2 ), 1.83-1.64 (m, 2H, CH 2 CH 2 OPh), 1.45-1.23 (m, 6H, 3×CH 2 ), 0.91 (t, 3H, J=6.8 Hz, CH 3 ).
[0448] 13 C NMR (50 MHz, CDCl 3 ) δ=166.9, 157.9, 148.1, 129.6, 129.3, 121.5, 114.6, 68.0, 51.4, 37.6, 31.5, 29.2, 25.7, 22.5, 14.0.
[0449] MS (ESI) m/z (%): 277 [M+H, 100] + .
Methyl 4-(4-(hexyloxy)phenyl)butanoate (34)
[0450] Procedure S
[0000]
[0451] C 17 H 26 O 3
[0452] MW: 278.39.
[0453] Colorless oil. Yield 91%.
[0454] 1 H NMR (200 MHz, CDCl 3 ) δ=7.08 (d, 2H, J=8.6 Hz, CH, Ph), 6.83 (d, 2H, J=8.6 Hz, CH, Ph), 3.93 (t, 2H, J=6.6 Hz, CH 2 OPh), 3.67 (s, 3H, COOCH 3 ), 2.60 (t, 2H, J=7.2 Hz, PhCH 2 ), 2.33 (t, 2H, J=7.2 Hz, CH 2 COOMe), 2.05-1.89 (m, 2H, CH 2 CH 2 COOMe), 1.86-1.71 (m, 2H, CH 2 CH 2 OPh), 1.54-1.23 (m, 6H, 3×CH 2 ), 0.92 (t, 3H, J=6.6 Hz, CH 3 ).
[0455] 13 C NMR (50 MHz, CDCl 3 ) δ=173.9, 157.4, 133.0, 129.2, 114.3, 67.9, 51.3, 34.1, 33.2, 31.5, 29.2, 26.6, 25.7, 22.5, 13.9.
4-(4-(Hexyloxy)phenyl)butanal (35)
[0456] Procedure N then G
[0000]
[0457] C 16 H 24 O 2
[0458] MW: 248.36.
[0459] Yellow oil. Yield 99%.
[0460] 1 H NMR (200 MHz, CDCl 3 ) δ=9.76 (t, 1H, J=1.6 Hz, CHO), 7.08 (d, 2H, J=8.6 Hz, CH, Ph), 6.83 (d, 2H, J=8.6 Hz, CH, Ph), 3.94 (t, 2H, J=6.6 Hz, CH 2 OPh), 2.61 (t, 2H, J=7.4 Hz, PhCH 2 ), 2.49-2.37 (m, 2H, CH 2 CHO), 2.06-1.90 (m, 2H, CH 2 CH 2 CHO), 1.86-1.71 (m, 2H, CH 2 CH 2 OPh) 1.49-1.27 (m, 6H, 3×CH 2 ), 0.91 (t, 3H, J=6.8 Hz, CH 3 ).
[0461] 13 C NMR (50 MHz, CDCl 3 ) S=202.4, 157.4, 133.0, 129.2, 114.4, 68.0, 43.1, 34.1, 31.6, 29.3, 25.7, 23.8, 22.6, 14.0.
5-(4-(Hexyloxy)phenyl)-2-hydroxypentanenitrile (36)
[0462] Procedure T
[0000]
[0463] C 17 H 25 NO 2
[0464] MW: 275.39.
[0465] Colorless oil. Yield 74%.
[0466] 1 H NMR (200 MHz, CDCl 3 ) δ=7.08 (d, 2H, J=8.8 Hz, CH, Ph), 6.83 (d, 2H, J=8.8 Hz, CH, Ph), 4.43 (t, 1H, J=6.2 Hz, CHOH), 3.94 (t, 2H, J=6.6 Hz, CH 2 OPh), 2.63 (t, 2H, J=6.4 Hz, PhCH 2 ), 2.28 (br s, 1H, OH), 1.93-1.61 (m, 6H, 3×CH 2 ), 1.53-1.23 (m, 6H, 3×CH 2 ), 0.91 (t, 3H, J=6.8 Hz, CH 3 ).
[0467] 13 C NMR (50 MHz, CDCl 3 ) δ=157.4, 132.9, 129.2, 119.9, 114.5, 68.0, 61.0, 34.5, 34.0, 31.5, 29.2, 26.3, 25.7, 22.5, 14.0.
[0468] MS (ESI) m/z (%): 293 [M+H 2 O, 100] + .
Methyl 5-(4-(hexyloxy)phenyl)-2-hydroxypentanoate (37)
[0469] Procedure U
[0000]
[0470] C 18 H 28 O 4
[0471] MW: 308.41.
[0472] Colorless oil. Yield 86%.
[0473] 1 H NMR (200 MHz, CDCl 3 ) δ=7.08 (d, 2H, J=8.6 Hz, CH, Ph), 6.81 (d, 2H, J=8.6 Hz, CH, Ph), 4.20 (t, 1H, J=6.8 Hz, CHOH), 3.93 (t, 2H, J=6.6 Hz, CH 2 OPh), 3.78 (s, 3H, COOCH 3 ), 3.00 (br s, 1H, CHOH), 2.58 (t, 2H, J=6.6 Hz, PhCH 2 ), 1.86-1.55 (m, 6H, 3×CH 2 ), 1.52-1.17 (m, 6H, 3×CH 2 ), 0.91 (t, 3H, J=6.6 Hz, CH 3 ).
[0474] 13 C NMR (50 MHz, CDCl 3 ) δ=175.5, 157.2, 133.7, 129.1, 114.3, 70.3, 67.9, 52.4, 34.5, 33.8, 31.5, 29.2, 26.7, 25.7, 22.5, 14.0.
[0475] MS (ESI) m/z (%): 309 [M+H, 100] + .
Methyl 2-fluoro-5-(4-(hexyloxy)phenyl)pentanoate (38)
[0476] Procedure P
[0000]
[0477] C 18 H 27 FO 3
[0478] MW: 310.40.
[0479] Colorless oil. Yield 37% (182 mg).
[0480] 1 H NMR (200 MHz, CDCl 3 ) δ=7.08 (d, 2H, J=8.6 Hz, CH, Ph), 6.83 (d, 2H, J=8.8 Hz, CH, Ph), 4.93 (dt, 1H, J H-H =5.8 Hz, J H-F =50.2 Hz, CHF), 3.94 (t, 2H, J=6.6 Hz, CH 2 OPh), 3.79 (s, 3H, COOCH 3 ), 2.61 (t, 2H, J=7.4 Hz, PhCH 2 ), 2.05-1.62 (m, 6H, 3×CH 2 ), 1.56-1.23 (m, 6H, 3×CH 2 ), 0.91 (t, 3H, J=6.6 Hz, CH 3 ).
[0481] 13 C NMR (50 MHz, CDCl 3 ) δ=170.3 (d, =23 Hz, COO), 157.4, 133.2, 129.2, 114.4, 88.8 (d, J C-F =183 Hz, CF), 68.0, 52.3, 34.3, 32.0, 31.6, 29.3, 26.3, 25.7, 22.6, 14.0.
[0482] 19 F NMR (186 MHz, CDCl 3 ) δ=−192.4 (m, CHF).
[0483] MS (ESI) m/z (%): 328 [M+H 2 O, 100] + , 311 [M+H, 15] + .
2-Fluoro-5-(4-(hexyloxy)phenyl)pentanal (39)
[0484] Procedure N then Q
[0000]
[0485] C 17 H 25 FO 2
[0486] MW: 280.38.
[0487] Yellow oil. Yield 50%.
[0488] 1 H NMR (200 MHz, CDCl 3 ) δ=9.74 (d, 1H, J=6.2 Hz, CHO), 7.08 (d, 2H, J=8.4 Hz, CH, Ph), 6.84 (d, 2H, J=8.4 Hz, CH, Ph), 4.76 (dm, 1H, J H-F =51.4 Hz, CHF), 3.94 (t, 2H, J=6.6 Hz, CH 2 OPh), 2.62 (t, 2H, J=7.2 Hz, PhCH 2 ), 1.93-1.72 (m, 6H, 3×CH 2 ), 1.54-1.24 (m, 6H, 3×CH 2 ), 0.93 (t, 3H, J=6.6 Hz, CH 3 ).
[0489] 13 C NMR (50 MHz, CDCl 3 ) δ=200.0 (d, J C-C-F =34 Hz, CHO), 157.4, 133.0, 129.2, 114.4, 94.8 (d, J C-F =178 Hz, CF), 67.9, 34.3, 31.5, 29.6 (d, J C-C-F =20 Hz, CH 2 CHF), 29.2, 26.1, 25.7, 22.6, 14.0.
[0490] 19 F NMR (186 MHz, CDCl 3 ) δ=−199.8 (m, CHF).
2-Fluoro-5-(4-(hexyloxy)phenyl)-1-(thiazol-2-yl)pentan-1-ol (40)
[0491] Procedure A
[0000]
[0492] C 20 H 28 FNO 2 S
[0493] MW: 365.51.
[0494] Yellow oil. Yield 38%.
[0495] 1 H NMR (200 MHz, CDCl 3 ) δ=7.90 (d, 1/7H, J=3.2 Hz, ArH), 7.83 (d, 6/7H, J=3.2 Hz, ArH), 7.45 (d, 1/7H, J=3.2 Hz, ArH), 7.35 (d, 6/7H, J=3.2 Hz, ArH), 7.05 (d, 2H, J=8.6 Hz, CH, Ph), 6.80 (d, 2H, J=8.6 Hz, CH, Ph), 5.15 (dd, 1H, J H-H =4.6 Hz, J H-F =12.8 Hz, CHOH), 4.99-4.65 (dm, 1H, J H-F =48.2 Hz, CHF), 3.93 (t, 2H, J=6.4 Hz, CH 2 OPh), 2.56 (t, 2H, J=7.2 Hz, PhCH 2 ), 1.88-1.27 (m, 12H, 6×CH 2 ), 0.91 (t, 3H, J=6.8 Hz, CH 3 ).
[0496] 13 C NMR (50 MHz, CDCl 3 ) δ=170.2, 157.2, 142.1, 133.7, 129.1, 119.7, 114.3, 95.1 (d, J C-F =174 Hz, CF), 73.0 (d, ⅓C, J C-C-F =21 Hz, COH), 72.9 (d, ⅔C, J C-C-F =24 Hz, COH), 67.9, 34.5, 31.5, 30.4 (d, J C-C-F =20 Hz, CH 2 ), 29.2, 26.9, 25.7, 22.5, 14.0.
[0497] 19 F NMR (186 MHz, CDCl 3 ) δ=−190.0 (m, CHF), −194.4 (m, CHF).
[0498] MS (ESI) m/z (%): 366 [M+H, 100] + .
2-Fluoro-5-(4-(hexyloxy)phenyl)-1-(thiazol-2-yl)pentan-1-one (41)
[0499] Procedure B
[0000]
[0500] C 20 H 26 FNO 2 S
[0501] MW: 363.49.
[0502] Colorless oil. Yield 60%.
[0503] 1 H NMR (200 MHz, CDCl 3 ) δ=8.04 (d, 1H, J=2.8 Hz, ArH), 7.75 (d, 1H, J=3.0 Hz, ArH), 7.07 (d, 2H, J=8.4 Hz, CH, Ph), 6.80 (d, 2H, J=8.6 Hz, CH, Ph), 5.98 (ddd, 1H, J H-F =49.6 Hz, J H-H =7.6 Hz, J H-H =3.6 Hz, CHF), 3.92 (t, 2H, J=6.6 Hz, CH 2 OPh), 2.75-2.52 (m, 2H, PhCH 2 ), 2.30-1.70 (m, 6H, 3×CH 2 ), 1.59-1.26 (m, 6H, 3×CH 2 ), 0.91 (t, 3H, J=6.6 Hz, CH 3 ).
[0504] 13 C NMR (50 MHz, CDCl 3 ) δ=188.9 (d, =19 Hz, CO), 163.8, 157.4, 145.1, 133.3, 129.2, 126.9, 114.4, 92.3 (d, J C-F =182 Hz, CF), 68.0, 34.3, 32.0 (d, J C-C-F =21 Hz, CH 2 CHF), 31.6, 29.3, 26.6, 25.7, 22.6, 14.0.
[0505] 19 F NMR (186 MHz, CDCl 3 ) δ=−196.2 (m, CHF).
[0506] MS (ESI) m/z (%): 364 [M+H, 100] + .
[0507] The following new target compounds are therefore synthesised
[0000]
TABLE 1
2-Oxo-thiazoles.
Corres
Number
No.
Structure
MW
ClogP
GK146
3a
323.54
8.1
GK147
3b
245.34
3.7
GK149
3d
371.58
8.3
GK150
9
317.45
5.4
GK151
15a
395.60
8.3
GK152
15b
317.40
3.8
GK153
19
345.50
6.3
GK154
24
359.53
7.1
GK155
29
341.53
7.8
GK156
41
363.49
6.0
[0508] A series of further compounds have been synthesised based on the principles outlined above. These are listed in table 2
[0000]
TABLE 2
GK148
GK157
GK158
GK159
GK160
GK162
GK179
GK180
GK181
GK182
GK183
GK184
GK198
GK199
GK201
GK202
GK203
GK204
Synthetic Schemes
[0509]
[0000]
[0000]
Characterization Data
[0510] The following target compounds of the invention are synthesised according to the protocols above:
N-methoxy-N-methyloleamide (4c)
[0511] Prepared by Procedure C
[0000]
[0512] C 20 H 39 NO 2
[0513] MW: 325.53
[0514] Colorless oil. Yield 86% (985 mg).
[0515] 1 H NMR (200 MHz, CDCl 3 ) δ=5.34-5.29 (m, 2H, CH═CH), 3.65 (s, 3H, OMe), 3.15 (s, 3H, NMe), 2.38 (t, 2H, J=7.4 Hz, CH 2 CO), 1.99 (m, 4H, CH 2 CH═CHCH 2 ), 1.60 (m, 2H, CH 2 CH 2 CO), 1.29-1.24 (m, 20H, 10×CH 2 ), 0.85 (t, 3H, J=5.2 Hz, CH 3 ).
[0516] 13 C NMR (50 MHz, CDCl 3 ) δ=174.5, 129.8, 129.6, 61.0, 31.8, 29.6, 29.6, 29.4, 29.3, 29.2, 27.0, 25.5, 24.5, 22.5, 14.0.
N-methoxy-N-methyl-5-(naphthalen-2-yl)pentanamide (4e)
[0517] Prepared by Procedure C
[0000]
[0518] C 17 H 21 NO 2
[0519] MW: 271.35
[0520] Colorless oil. Yield 75% (310 mg).
[0521] 1 H NMR (CDCl 3 ): =7.90-7.30 (m, 7H, ArH), 3.65 (s, 3H, OMe), 3.18 (s, 3H, NMe), 2.82 (t, 2H, J=7.2 Hz, CH 2 ), 2.47 (t, 2H, J=7.0 Hz, CH 2 ), 1.98-1.60 (m, 4H, 2×CH 2 ).
[0522] MS (ESI) m/z (%): 272 [M+H, 100] + .
(Z)-1-morpholinooctadec-9-en-1-one (5c)
[0523] Prepared by Procedure D
[0000]
[0524] C 22 H 41 NO 2
[0525] MW: 351.57
[0526] Colorless oil. Yield 98% (1.59 g).
[0527] 1 H NMR (200 MHz, CDCl 3 ) δ=5.31-5.25 (m, 2H, CH═CH), 3.62-3.57 (m, 6H, CH 2 OCH 2 , CHHNCHH), 3.40 (t, 2H, J=5.0 Hz, CHHNCHH), 2.25 (t, 2H, J=7.4 Hz, CH 2 CO), 1.97-1.93 (m, 4H, CH 2 CH═CHCH 2 ), 1.60-1.53 (m, 2H, CH 2 CH 2 CO), 1.26-1.21 (m, 20H, 10×CH 2 ), 0.82 (t, 3H, J=6.2 Hz, CH 3 ).
[0528] 13 C NMR (50 MHz, CDCl 3 ) δ=171.6, 129.8, 129.5, 66.8, 66.5, 45.8, 41.7, 32.9, 31.7, 29.6, 29.5, 29.3, 29.2, 29.1, 28.9, 27.0, 25.0, 22.5, 13.9.
(Z)-1-(Thiazol-2-yl)octadec-9-en-1-one (3c)
[0529] Prepared by Procedure E
[0530] Yield when the Weinreb amide was used: 70%
[0531] Yield when the morpholine amide was used: 70%
5-(Naphthalen-2-yl)-1-(thiazol-2-yl)pentan-1-one (3e)
[0532] Prepared by Procedure E
[0000]
[0533] C 18 H 17 NOS
[0534] MW: 295.40
[0535] Yellow solid. Yield 70%
[0536] 1 H NMR (200 MHz, CDCl 3 ) δ=7.97 (d, 1H, J=3.0 Hz, ArH), 7.80-7.75 (m, 3H, ArH), 7.75-7.63 (m, 2H, ArH), 7.50-7.30 (m, 3H, ArH), 3.21 (t, 2H, J=7.0 Hz, CH 2 ), 2.83 (t, 2H, J=6.8 Hz, CH 2 ), 1.98-1.80 (m, 4H, 2×CH 2 ).
[0537] 13 C NMR (50 MHz, CDCl 3 ) δ=193.8, 167.1, 144.6, 139.6, 133.5, 131.9, 127.8, 127.5, 127.4, 127.3, 126.3, 126.1, 125.8, 125.0, 38.2, 35.7, 30.8, 23.6.
[0538] MS (ESI) m/z (%): 296 [M+H, 100] + .
1-(Benzo[d]thiazol-2-yl)hexadecan-1-one (6a)
[0539] Prepared by Procedure E
[0000]
[0540] C 23 H 35 NOS
[0541] MW: 373.60
[0542] Yellowish solid.
[0543] Yield via Weinreb amide 60% (140 mg).
[0544] Yield via morpholine amide 85% (180 mg).
[0545] m.p.: 74-76° C.
[0546] 1 H NMR (200 MHz, CDCl 3 ) δ=8.19 (d, 1H, J=7.4 Hz, benzothiazole), 7.98 (d, 1H, J=7.4 Hz, benzothiazole), 7.62-7.49 (m, 2H, benzothiazole), 3.27 (t, 2H, J=7.2 Hz, CH 2 CO), 1.86-1.74 (m, 2H, CH 2 CH 2 CO), 1.44-1.21 (m, 24H, 12×CH 2 ), 0.88 (t, 3H, J=6.0 Hz, CH 3 ).
[0547] 13 C NMR (50 MHz, CDCl 3 ) δ=195.6, 166.6, 153.5, 137.2, 127.5, 126.8, 125.3, 122.4, 38.5, 31.9, 29.6, 29.6, 29.4, 29.3, 29.3, 29.1, 23.9, 22.6, 14.1.
[0548] MS (ESI) m/z (%): 374 [M+H, 100] + .
1-(Benzo[d]thiazol-2-yl)-5-phenylpentan-1-one (6b)
[0549] Prepared by Procedure E
[0000]
[0550] C 18 H 17 NOS
[0551] MW: 295.40
[0552] Yellow solid.
[0553] Yield via Weinreb amide 77% (204 mg).
[0554] Yield via morpholine amide 72% (126 mg).
[0555] m.p.: 66-68° C.
[0556] 1 H NMR (200 MHz, CDCl 3 ) δ=8.19 (d, 1H, J=7.4 Hz, benzothiazole), 7.96 (d, 1H, J=7.6 Hz, benzothiazole), 7.61-7.47 (m, 2H, benzothiazole), 7.34-7.15 (m, 5H, Ph), 3.31 (t, 2H, J=6.8 Hz, CH 2 CO), 2.70 (t, 2H, J=7.4 Hz, PhCH 2 ), 1.96-1.69 (m, 4H, 2×CH 2 ).
[0557] 13 C NMR (50 MHz, CDCl 3 ) δ=195.2, 166.3, 153.4, 142.0, 137.1, 128.3, 128.2, 127.5, 126.8, 125.6, 125.2, 122.3, 38.2, 35.5, 30.8, 23.4.
[0558] MS (ESI) m/z (%): 296 [M+H, 100] + .
(Z)-1-(Benzo[d]thiazol-2-yl)octadec-9-en-1-one (6c)
[0559] Prepared by Procedure E
[0000]
[0560] C 25 H 37 NOS
[0561] MW: 399.63
[0562] Yellow oil.
[0563] Yield via Weinreb amide 70% (170 mg).
[0564] 1 H NMR (200 MHz, CDCl 3 ) δ=8.17 (d, 1H, J=7.0 Hz, benzothiazole), 7.95 (d, 1H, J=6.2 Hz, benzothiazole), 7.60-7.45 (m, 2H, benzothiazole), 5.42-5.27 (m, 2H, CH═CH), 3.26 (t, 2H, J=7.4 Hz, CH 2 CO), 2.02-2.00 (m, 4H, CH 2 CH═CHCH 2 ), 1.88-1.73 (m, 2H, CH 2 CH 2 CO), 1.43-1.25 (m, 20H, 10×CH 2 ), 0.87 (t, 3H, J=6.4 Hz, CH 3 ).
[0565] 13 C NMR (50 MHz, CDCl 3 ) δ=195.4, 166.5, 153.4, 137.1, 129.9, 129.6, 127.4, 126.8, 125.2, 122.3, 38.5, 31.8, 29.7, 29.6, 29.4, 29.2, 29.2, 29.1, 29.0, 27.1, 27.1, 23.8, 22.6, 14.0.
[0566] MS (ESI) m/z (%): 400 [M+H, 100] + .
1-(Benzo[d]thiazol-2-yl)-5-(naphthalen-2-yl)pentan-1-one (6e)
[0567] Prepared by Procedure E
[0000]
[0568] C 22 H 19 NOS
[0569] MW: 345.46
[0570] Yellow solid. Yield 72%.
[0571] 1 H NMR (200 MHz, CDCl 3 ) δ=8.20 (d, 1H, J=6.0 Hz, ArH), 7.97 (d, 1H, J=8.0 Hz, ArH), 7.90-7.70 (m, 3H, ArH), 7.70-7.30 (m, 6H, ArH), 3.35 (t, 2H, J=7.0 Hz, CH 2 ), 2.90 (t, 2H, J=6.8 Hz, CH 2 ), 2.05-1.82 (m, 4H, 2×CH 2 ).
[0572] 13 C NMR (50 MHz, CDCl 3 ) δ=195.3, 166.4, 153.5, 139.6, 137.2, 133.5, 131.9, 127.8, 127.6, 127.5, 127.4, 127.3, 126.9, 126.4, 125.8, 125.3, 125.0, 122.4, 38.3, 35.8, 30.7, 23.6.
[0573] MS (ESI) m/z (%): 246 [M+H, 100] + .
Ethyl 2-(2-(1-hydroxyhexadecyl)thiazol-4-yl)acetate (14c)
[0574] Prepared by Procedure K
[0000]
[0575] C 23 H 41 NO 3 S
[0576] MW: 411.64
[0577] White solid.
[0578] 1 H NMR (300 MHz, CDCl 3 ): δ=7.15 (s, 1H, SCH), 4.97 (dd, J, =7.8 Hz, J 2 =4.5 Hz, 1H, CHOH), 4.20 (q, J=7.2 Hz, 2H, COOCH 2 ), 3.82 (s, 2H, CH 2 COO), 2.07-1.78 (m, 2H CH 2 ), 1.59-1.20 (m, 29H, 13×CH 2 , CH 3 ), 0.89 (t, J=6.3 Hz, 3H, CH 3 ).
[0579] 13 C NMR (50 MHz, CDCl 3 ): δ=174.98, 170.36, 148.18, 115.97, 71.95, 61.08, 38.32, 36.93, 31.91, 29.68, 29.66, 29.56, 29.49, 29.36, 25.20, 22.69, 14.14.
[0580] MS (ESI) m/z (%): 412 [M+H, 100] + .
Ethyl 2-(2-(1-hydroxy-5-phenylpentyl)thiazol-4-yl)acetate (14d)
[0581] Prepared by Procedure K
[0000]
[0582] C 18 H 23 NO 3 S
[0583] MW: 333.45
[0584] Pale yellow solid; Yield 44%.
[0585] m.p. 53-55° C.
[0586] 1 H NMR (200 MHz, CDCl 3 ): δ 7.35-7.07 (m, 6H, SCH, Ph), 4.93 (dd, J, =7.8 Hz, J 2 =4.8 Hz, 1H, CHOH), 4.18 (q, J=7.0 Hz, COOCH 2 ), 3.79 (s, 2H, CH 2 COO), 2.61 (t, J=7.2 Hz, CH 2 Ph), 2.06-1.37 (m, 6H, 3×CH 2 ), 1.26 (t, J=7.2 Hz, 3H, CH 3 ).
[0587] 13 C NMR (50 MHz, CDCl 3 ) δ 174.95, 170.37, 148.20, 142.38, 128.34, 128.24, 125.65, 116.00, 71.80, 61.08, 38.12, 36.90, 35.74, 31.19, 24.89, 14.15.
[0588] MS (ESI) m/z (%): 334 [M+H, 100] + .
Ethyl 2-(2-palmitoylthiazol-4-yl)acetate (15c)
[0589] Prepared by Procedure B
[0000]
[0590] C 23 H 39 NO 3 S
[0591] MW: 409.63
[0592] White solid. Yield 90%.
[0593] m.p. 46-48° C.
[0594] 1 H NMR (300 MHz, CDCl 3 ): δ=7.54 (s, 1H, SCH), 4.21 (q, J=7.2 Hz, 2H, COOCH 2 ), ), 3.90 (s, 2H, CH 2 COO), 3.12 (t, J=7.5 Hz, 2H, CH 2 CO), 1.82-1.62 (m, 2H CH 2 ), 1.55-1.19 (m, 27H, 12×CH 2 , CH 3 ), 0.88 (t, J=7.0 Hz, 3H, CH 3 ).
[0595] 13 C NMR (50 MHz, CDCl 3 ): δ=194.09, 170.00, 166.52, 150.95, 123.56, 61.24, 38.43, 37.00, 31.91, 29.65, 29.47, 29.39, 29.35, 29.18, 23.91, 22.68, 14.13.
[0596] MS (ESI) m/z (%): 410 [M+H, 100] + .
Ethyl 2-(2-(5-phenylpentanoyl)thiazol-4-yl)acetate (15d)
[0597] Prepared by Procedure B
[0000]
[0598] C 18 H 21 NO 3 S
[0599] MW: 331.43
[0600] White oil. Yield 81%.
[0601] 1 H NMR (300 MHz, CDCl 3 ): δ=7.55 (s, 1H, SCH), 7.34-7.16 (m, 5H, Ph), 4.22 (q, J=7.2 Hz, 2H, COOCH 2 ), 3.91 (s, 2H, CH 2 COO), 3.17 (t, J=7.5 Hz, 2H, CH 2 CO), 2.68 (t, J=7.2 Hz, 2H, CH 2 Ph), 1.85-1.63 (m, 4H 2×CH 2 ), 1.30 (t, J=7.2 Hz, 3H, CH 3 ).
[0602] 13 C NMR (50 MHz, CDCl 3 ): δ=193.82, 169.99, 166.42, 150.99, 142.17, 128.39, 128.27, 125.71, 123.69, 61.26, 38.17, 36.99, 35.65, 30.92, 23.56, 14.16.
[0603] MS (ESI) m/z (%): 332 [M+H, 99] + .
Ethyl 2-(2-(5-(biphenyl-4-yl)pentanoyl)thiazol-4-yl)acetate (15e)
[0604] Prepared by Procedure B
[0000]
[0605] C 24 H 25 NO 3 S
[0606] MW: 407.53
[0607] White solid.
[0608] 1 H NMR (200 MHz, CDCl 3 ): δ=7.65-7.18 (m, 10H, Ar, SCH), 4.21 (q, J=7.4 Hz, 2H, COOCH 2 ), 3.90 (s, 2H, CH 2 COO), 3.18 (t, J=6.6 Hz, CH 2 CO), 2.70 (t, J=7.2 Hz, CH 2 Ph), 1.94-1.65 (m, 4H, 2×CH 2 ), 1.28 (t, J=7.2 Hz, CH 3 ).
[0609] 13 C NMR (50 MHz, CDCl 3 ): δ=193.79, 169.95, 166.40, 151.01, 141.29, 141.06, 138.66, 128.80, 128.66, 127.01, 126.95, 123.67, 61.22, 38.15, 36.97, 35.25, 30.85, 23.57, 14.14.
[0610] MS (ESI) m/z (%): 408 [M+H, 100] + .
2-palmitoylthiazole-4-carboxylic acid (15′a)
[0611] Prepared by Procedures L, then B
[0000]
[0612] C 20 H 33 NO 3 S
[0613] MW: 367.55
[0614] White solid. Yield 50%.
[0615] m.p. 98-100° C.
[0616] 1 H NMR (200 MHz, CDCl 3 ): δ=8.39 (s, 1H, CH), 3.25-3.00 (m, 2H, CH 2 ), 1.80-1.55 (m, 2H, CH 2 ), 1.40-1.00 (m, 24H, 12×CH 2 ), 0.88 (t, 3H, J=6.8 Hz, CH 3 ).
[0617] 13 C NMR (50 MHz, CDCl 3 +CD 3 OD): δ=193.9, 166.4, 164.6, 151.5, 131.8, 37.9, 31.5, 29.2, 29.0, 28.9, 28.7, 23.2, 22.2, 13.4.
[0618] MS (ESI) m/z (%): 366 [M−H, 100] − .
2-(5-Phenylpentanoyl)thiazole-4-carboxylic acid (15′b)
[0619] Prepared by Procedure M
[0000]
[0620] C 15 H 15 NO 3 S
[0621] MW: 289.35
[0622] White solid. Yield 86% (25 mg).
[0623] 1 H NMR (CDCl 3 ): δ=8.55 (s, 2H, ArH, COOH), 7.30-7.10 (m, 5H, Ph), 3.26 (t, 2H, J=6.8 Hz, CH 2 ), 2.66 (t, 2H, J=7.0 Hz, CH 2 ), 1.90-1.63 (m, 4H, 2×CH 2 ).
[0624] 13 C NMR (CDCl 3 ): δ=193.5, 167.8, 164.6, 147.4, 142.0, 134.9, 128.4, 128.3, 125.8, 38.2, 35.6, 30.7, 23.2.
[0625] MS (ESI) m/z (%): 290 [M+H, 47] + .
2-(2-Palmitoylthiazol-4-yl)acetic acid (15′c)
[0626] Prepared by Procedures L, then B
[0000]
[0627] C 21 H 35 NO 3 S
[0628] MW: 381.57
[0629] White solid.
[0630] 1 H NMR (300 MHz, CDCl 3 ): δ 7.55 (s, 1H, SCH), 3.98 (s, 2H, CH 2 COO), 3.13 (t, J=7.6 Hz, 2H, CH 2 CO), 1.82-1.69 (m, 2H, CH 2 ), 1.43-1.18 (m, 24H, 12×CH 2 ), 0.89 (t, J=6.9 Hz, 3H, CH 3 ).
[0631] MS (ESI) m/z (%): 336 [M-COOH—H, 100] − , 380 [M−H, 46] − .
2-(2-(5-Phenylpentanoyl)thiazol-4-yl)acetic acid (15′d)
[0632] Prepared by Procedure M
[0000]
[0633] C 16 H 17 NO 3 S
[0634] MW: 303.38
[0635] White oil. Yield 89%.
[0636] 1 H NMR (300 MHz, CDCl 3 ): δ 7.49 (s, 1H, SCH), 7.35-7.08 (m, 5H, Ph), 3.88 (s, 2H, CH 2 COO), 3.11 (t, J=7.5 Hz, 2H, CH 2 CO), 2.63 (t, J=7.0 Hz, 2H, CH 2 Ph), 1.85-1.63 (m, 4H 2×CH 2 ).
[0637] MS (ESI) m/z (%): 304 [M+H, 77] + .
(S)-tert-Butyl 4-(benzyloxycarbonylamino)-5-(methoxy(methyl)amino)-5-oxopentanoate (43b)
[0638] Prepared by Procedure C
[0000]
[0639] C 19 H 28 N 2 O 6
[0640] MW: 380.44
[0641] Colorless oil. Yield 100%.
[0642] 1 H NMR (200 MHz, CDCl 3 ) δ=7.35-7.20 (m, 5H, ArH), 5.67 (d, 1H, J=8.0 Hz, NH), 5.06 (s, 2H, CH 2 ), 4.80-4.60 (m, 1H, CH), 3.73 (s, 3H, OMe), 3.15 (s, 3H, NMe), 2.40-1.70 (m, 4H, CH 2 ), 1.38 (s, 9H, t Bu).
[0643] 13 C NMR (50 MHz, CDCl 3 ) δ=171.9, 155.9, 136.1, 128.3, 127.9, 127.8, 80.3, 66.6, 61.4, 50.3, 31.9, 31.0, 27.9, 27.4.
[0644] MS (ESI) m/z (%): 381 [M+H, 100] + .
(S)-tert-Butyl 5-(methoxy(methyl)amino)-5-oxo-4-(2-phenylacetamido)pentanoate (45b)
[0645] Prepared by Procedures V, then W
[0000]
[0646] C 19 H 28 N 2 O 5
[0647] MW: 364.44
[0648] Colorless oil.
[0649] 1 H NMR (200 MHz, CDCl 3 ) δ=7.40-7.20 (m, 5H, ArH), 6.38 (d, 1H, J=8.0 Hz, NH), 5.02-4.90 (m, 1H, CH), 3.65 (s, 3H, OMe), 3.55 (s, 2H, CH 2 ), 3.18 (s, 3H, NMe), 2.25-1.70 (m, 4H, CH 2 ), 1.40 (s, 9H, t Bu).
[0650] 13 C NMR (50 MHz, CDCl 3 ) δ=172.1, 170.9, 166.3, 134.6, 129.3, 128.9, 127.2, 80.5, 61.6, 48.7, 43.6, 31.1, 28.0, 27.2.
[0651] MS (ESI) m/z (%): 365 [M+H, 100] + .
N-(2-(Benzo[d]thiazol-2-yl)-2-oxoethyl)-2-phenylacetamide (46a)
[0652] Prepared by Procedure E
[0000]
[0653] C 17 H 14 N 2 O 2 S
[0654] MW: 310.37
[0655] Orange solid.
[0656] 1 H NMR (200 MHz, CDCl 3 ) δ=8.11 (d, 1H, J=8.0 Hz, ArH), 7.94 (d, 1H, J=8.0 Hz, ArH), 7.65-7.40 (m, 2H, ArH), 7.39-7.20 (m, 5H, ArH), 6.34 (b, 1H, NH), 4.95 (d, 2H, J=5.2 Hz, CH 2 ), 3.67 (s, 2H, CH 2 ).
[0657] 13 C NMR (50 MHz, CDCl 3 ) δ=189.7, 171.4, 163.1, 153.3, 136.9, 134.4, 129.5, 129.0, 128.1, 127.4, 127.1, 125.6, 122.3, 46.8, 43.5.
[0658] MS (ESI) m/z (%): 311 [M+H, 100] + .
(S)-tert-Butyl 5-(benzo[d]thiazol-2-yl)-5-oxo-4-(2-phenylacetamido)pentanoate (46b)
[0659] Prepared by Procedure E
[0000]
[0660] C 24 H 26 N 2 O 4 S
[0661] MW: 438.54
[0662] Colorless Oil. Yield 50%.
[0663] 1 H NMR (200 MHz, CDCl 3 ) δ=8.10 (d, 1H, J=8.0 Hz, ArH), 7.91 (d, 1H, J=8.0 Hz, ArH), 7.62-7.20 (m, 7H, ArH), 6.77 (d, 1H, J=8.0 Hz, NH), 5.68-5.70 (m, 1H, CH), 3.61 (s, 2H, CH 2 ), 2.50-1.98 (m, 4H, CH 2 ), 1.38 (s, 9H, t Bu).
[0664] 13 C NMR (50 MHz, CDCl 3 ) δ=192.5, 172.1, 170.9, 163.5, 153.2, 137.0, 134.4, 129.3, 128.8, 127.9, 127.2, 127.0, 125.8, 122.2, 80.7, 55.1, 43.4, 30.3, 30.6, 27.9, 27.3.
[0665] MS (ESI) m/z (%): 439 [M+H, 55] + .
(S)-5-(Benzo[d]thiazol-2-yl)-5-oxo-4-(2-phenylacetamido)pentanoic acid (47)
[0666] Prepared by Procedure X
[0000]
[0667] C 20 H 18 N 2 O 4 S
[0668] MW: 382.43
[0669] Yellow solid. Yield 50%.
[0670] 1 H NMR (200 MHz, CDCl 3 ) δ=8.11 (d, 1H, J=8.0 Hz, ArH), 7.94 (d, 1H, J=8.0 Hz, ArH), 7.65-7.40 (m, 2H, ArH), 7.38-7.10 (m, 5H, ArH), 6.71 (d, 1H, J=8.0 Hz, NH), 5.90-5.60 (m, 1H, CH), 3.63 (s, 2H, CH 2 ), 2.55-2.25 (m, 3H, CH 2 ), 2.20-1.90 (m, 1H, CH 2 ).
[0671] 13 C NMR (50 MHz, CDCl 3 ) δ=192.3, 177.0, 171.6, 163.3, 153.3, 137.1, 134.2, 129.4, 129.0, 128.2, 127.5, 127.2, 126.1, 125.8, 122.3, 55.2, 43.5, 30.1, 27.5.
[0672] MS (ESI) m/z (%): 381 [M−H, 100] − .
[0673] Some of the compounds above were tested using an in vitro cPLA 2 enzyme activity assay.
[0674] In Vitro cPLA2 Assay
[0675] Assay for cPLA2 activity was performed by the use of sonicated vesicles of 1-palmitoyl-2-arachidonoyl-sn-glycerol-3-phosphorylcholine (100 μM) containing 100,000 cpm of 1-palmitoyl-2-[1 14C]arachidonoylsn-glycerol-3-phosphorylcholine in 100 mM Hepes, pH 7.5, 80 μM Ca2, 2 mM dithiothreitol, and 0.1 mg/ml BSA as described. Following a 35-min incubation at 37° C., the reaction was terminated (derived from Wijkander et al). The lower phase was separated by thin layer chromatography, and the spot corresponding to free [1-14C]arachidonic acid was visualized by digital imaging and quantified with a PhosphorImager (Fuji Instruments). The source of cPLA 2 enzyme was recombinant overexpression of the human gene for group IVa PLA2 in baculovirus insect cell expression system, as described in Abdullah et al.
Wijkander, J., and Sundler, R. (1991) Eur. J. Biochem. 202, 873-880 Abdullah, K., et al. (1995) Human cytosolic phospholipase A2 expressed in insect cells is extensively phosphorylated on Ser-505. Biochim Biophys Acta. 1995 May 11; 1244(1):157-64.
[0678] The results are presented below:
[0000]
Compound No.
Enzyme Assay IC 50
3b
3050 nM
24
3650 nM
41
3700 nM
[0679] Further Testing was Carried Out as Follows:
[0680] Reagents
[0681] The Cell Culture SW982 model cell line at a confluent or spheroid state (Wada Y, 2005) was used since gene expression and generation of proinflammatory cytokines resemble RA-derived synovial fibroblast-like cells.
[0682] AA release assay: 1 h preincubation at 50 and 25 μM-4 h IL-1B stimulation, repeated 2-3 times. Only inhibitors that showed a ˜50% inhibition in either of the initial two concentrations were further tested in a dose-response. IC50 is evaluated from dose-response inhibtions curves.
[0683] PGE2 Analysis
[0684] PGE 2 Detection
[0685] Samples and controls were slowly thawed and diluted (between 1:1 and 1:2500) in the standard diluent. The maximal dilution was 1:10 for one step. That is why several intermediate dilutions were prepared. In the beginning all values were determined from duplicates. After having minimized technical errors, samples were only analyzed as individuals. All further steps, except for some minor corrections, were performed according to the manufacturer's recommendations as can be found in the manual of the EIA kit. In order to optimize the results, the incubation time of the alkaline phosphatase substrate was prolonged by 15 minutes. During the incubation, the plates were kept in the dark. An example of the arrangements of the samples and controls is illustrated in the appendix. The read-out was carried out with a Multiscan plate reader (Ascent Labsystems) at wavelengths of 414 and 595 nm after 10 seconds shaking at 120 rpm. The corresponding software to obtain the data was the Ascent software for Multiscan, Version 2.4.1.
[0686] Data were processed using Microsoft Office Excel 2003 and SigmaPlot 10.0.
[0000]
AA
release
cPLA2
5W982
in vitro
cells
assay
IC50
IC50
PGE2-assay
Code
Structure
(μm)
(μm)
% inhibition
GK150
5.8
Not yet known
GK152
7.4 (2 h) >25 (4 h)
>5
0.1 uM:41% 3 uM::38% 10 uM::30% 30 uM:31%
GK159
<2 (2 h) ~25 (4 h)
>5
0.3 uM::76% 3 uM:18% 10 uM:23% 30 uM:10%
GK160
4.9
7.2
10 uM:12% 30 uM:30%
GK181
1.4
10 uM:16.3% 30 uM:22.5%
GK185
2.8
2
Not yet known
Other Embodiments
[0687] From the foregoing description, it will be apparent that variations and modifications may be made to the invention described herein to adopt it to various usages and conditions. Such embodiments are also within the scope of the following claims.
[0688] The recitation of a listing of elements in any definition of a variable herein includes definitions of that variable as any single element or combination (or subcombination) of listed elements. The recitation of an embodiment herein includes that embodiment as any single embodiment or in combination with any other embodiments or portions thereof.
[0689] All patents and publications mentioned in this specification are herein incorporated by reference to the same extent as if each independent patent and publication was specifically and individually indicated to be incorporated by reference. | The invention provides compounds of formula (I)
wherein X is O or S;
R 1 is H, OH, SH, nitro, NH 2 , NHC 1-6 alkyl, N(C 1-6 alkyl) 2 , halo, haloC 1-6 alkyl, CN, C 1-6 -alkyl, OC 1-6 alkyl, C 1-6 alkylCOOH, C 1-6 alkylCOOC 1-6 alkyl, C 2-6 -alkenyl, C 3-10 cycloalkyl, C 6-10 aryl, C 1-6 alkylC 6-10 aryl, heterocyclyl, heteroaryl, CONH 2 , CONHC 1-6 alkyl, CON(C 1-6 alkyl) 2 , OCOC 1-6 alkyl, or is an acidic group, such as a group comprising a carboxyl, phosphate, phosphinate, sulfate, sulfonate, or tetrazolyl group;
R 2 is as defined for R 1 or R 1 and R 2 taken together can form a 6-membered aromatic ring optionally substituted by up to 4 groups R 5 ;
R 3 is H, halo (preferably fluoro), or CHal 3 (preferably CF 3 );
each R 5 is defined as for R 1 ;
V 1 is a covalent bond or a C 1-20 alkyl group, or C 2-20 -mono or multiply unsaturated alkenyl group; said alkyl or alkenyl groups being optionally interupted by one or more heteroatoms selected from O, NH, N(C 1-6 alkyl), S, SO, or SO 2 ;
M 1 is absent or is a C 5-10 cyclic group or a C 5-15 aromatic group; and
R 4 is H, halo, OH, CN, nitro, NH 2 , NHC 1-6 alkyl, N(C 1-6 alkyl) 2 , haloC 1-6 alkyl, a C 1-20 alkyl group, or C 2-20 -mono or multiply unsaturated alkenyl group, said C 1-20 alkyl or C 2-20 alkenyl groups being optionally interupted by one or more heteroatoms selected from O, NH, N(C 1-6 alkyl), S, SO, or SO 2 ;
with the proviso that the group V 1 M 1 R 4 as a whole provides at least 4 backbone atoms from the C(R 3 ) group;
or a salt, ester, solvate, N-oxide, or prodrug thereof; for use in the treatment of a chronic inflammatory condition. | 2 |
BACKGROUND OF THE INVENTION
This invention relates to a method of oxidizing organic thiol compounds to disulfide compounds by the use of xanthides.
Thiols have been oxidized by biological oxidants such as flavins, cytochroms, and dehydroascorbic acid [G. E. Woodward, Biochem. J. 27: 1411 (1933)]; by inorganic chemicals such as iodine, hydrogen peroxide, potassium ferricyanide, and nitric acid (Kirk-Othmer Encyclopedia of Chemical Technology, Second Edition, Vol. 20, Interscience Publishers, New York, New York, 1969, pages 208-209); and by radiation using X-rays, β-rays , and γ-rays (P.C. Jocelyn, Biochemistry of the SH Group, Academic Press, 1972, page 102). However, most of these reagents are also capable of reacting with other oxidizable sites such as aldehyde and amino groups.
Thiols may also be oxidized by air, but considerable time is required and conditions vary for each thiol. Dimethyl sulfoxide has been used to convert thiols to disulfide, but this procedure requires heating the solution for 6-8 hr. at 60°-80° C. and the removal of byproducts and unreacted DMSO for isolation of the disulfide [C. N. Yiannios and J. V. Karabinos, J. Org. Chem. 28: 3246(1963)].
Organic sulfenyl chlorides have been reductively coupled to form symmetrical disulfides and sulfur-containing polymers [Kobayashi et al., J. Polym. Sci. 10: 3317-3327 (1972)].
We have found a new method for preparing disulfide compounds which comprises reacting a xanthide with an organic thiol, at least one of which is in solution in a suitable solvent, in the presence of an amount of tertiary amine sufficient to initiate the reaction, xanthide and organic thiol being present in a 1:2 molar ratio, respectively.
This method has the advantage of being easy, quick, and general. The reaction is easily taylored so that the byproducts are either volatile or insoluble. Thus, recovery of the essentially pure disulfide compound is simply a matter of filtration or drying. When the reaction utilizes insoluble xanthides in a bed or column, the method becomes a continuous process. Organic disulfide products are used in a variety of ways. Tetramethyl- and tetraethylthiuran disulfides and dimorpholine disulfide aid in the vulcanization of rubber. Cellulose disulfides, such as in cotton fibers which are crosslinked, give crease resistance to the material, However, aside from product use, the method itself is useful. Since the reaction is quantitative and applicable to essentially all thiol compounds, the method is useful in the analytical determination of thiols. Iodine oxidation is the usual analytical procedure for this determination, but iodine is reactive with many other functional groups including multiple bonds. The method can also be used in the petroleum industry where petroleum is "sweetened" by the oxidation of thiol to disulfide.
DETAILED DESCRIPTION OF THE INVENTION
The preparation of unsymmetrical disulfides have been reported by Brois et al. [J. Amer. Chem. Soc. 92: 7629 (1970)]who induced the fragmentation of sulfenyl thiocarbonates with thiol compounds. Kobayashi et al. [Polym. Lett. Ed. 11: 225-228 (1973)]discloses the preparation of disulfide polymers from bis(oxycarbonyl) disulfides and dithiols.
Xanthide [i.e., dithiobis(thioformate) derivatives of organic compounds]starting materials of the invention include xanthides prepared by oxidative coupling xanthate derivatives of any organic compound capable of forming a xanthate derivative. Compounds of this type include alkyl alcohols ranging from methanol to fatty acid alcohols, starch, and cellulose, and compounds having other oxygen-, halogen-, nitrogen-, or sulfur-containing substituents.
The invention is also adaptable to essentially any organic thiol-containing compound including straight-chain, branched-chain, and cyclic alkyl thiols and substituted alkyl thiols such as methane thiols, dodecane thiols, isopropyl thiols, hexane thiols, amino acids, thioglycolic acids, hydroxy alkyl thiols, and fatty acid thiols; aryl and substituted aryl thiols such as benzyl thiol and phenyl thiol, p-chlorobenzene thiol and p-hydroxylbenzene thiol; alkyl dithiols such as 1,2-ethanedithiol and 1,4-butanedithiol; and polythiols such as thiol starch, thiol cellulose, protein (wool, enzymes), and polyvinyl thiol.
The preferred tertiary amines used in accordance with the invention include pyridine and triethylamine. However, with certain starting materials, inorganic bases such as sodium hydroxide can be used. The tertiary amines seem to act as catalysts and are needed only in amounts sufficient to initiate the reaction. Tertiary amines can also be suitable solvents for the reactants and are in these instances used in great excess of their reaction-initiating quantities.
Suitable solvents are those that will dissolve at least one of the reactants and will not interfere with the reaction (i.e., react with or prevent the reaction of either reactant). Preferably the solvent should also be sufficiently volatile to insure easy removal. Such solvents include water, pyridine, benzene, acetone, diethyl ether, methanol, and ethanol.
For the reaction to proceed quickly, only one of the two reactants need be in solution. In fact, in certain utilities, it is desirable to have one of the reactants insoluble in the solvent. Insoluble xanthides such as starch, crosslinked starch, and cellulose xanthides when placed in a bed or column react according to the invention with thiols in solutions which are percolated through the bed or column. In this manner a continuous feed of thiol solution results in a continuous elution of disulfide from the xanthide column. It is necessary to periodically regenerate the xanthide in the column by percolating a solution of alkali and carbon disulfide through the bed followed by a solution of sodium nitrite. Since carbon disulfide is given off by the xanthide-thiol reaction, it can be collected and used in the rexanthation process. The continuous process is possible because the reaction is almost instantaneous when the reactants come together at room temperatures (i.e., 25°-30° C.) in the presence of a tertiary amine.
Since the reaction is quantitative (i.e., xanthides and thiols react in a 1:2 molar ratio, respectively) and essentially instantaneous, it lends itself to an analytical procedure for determination of thiol groups. It is preferable to use a low molecular weight xanthide such as methyl xanthide, especially when analyzing a high molecular weight thiol such as starch or cellulose thiol.
The following examples are intended to further illustrate the invention and should not be construed as limiting the scope of the invention as defined by the claims.
PREPARATION OF XANTHIDE
Methyl xanthide [dimethyl dithiobis(thioformate)]: 25 g. of methanol were added to a solution of 30 g. of potassium hydroxide in 30 ml. of water. The mixture was cooled to 5° and treated with 30 ml. carbon disulfide. After stirring for 10 min., 25 g. of sodium nitrite was added. Then the pH was adjusted to about 3 with 30 percent acetic acid. The xanthide thus formed was extracted with ether. Evaporation of the ether gave 37 g. of methyl xanthide.
Starch xanthide containing 23 percent sulfur (0.8 degree of substitution) was prepared in the same manner.
EXAMPLE 1
To a solution of 1.4 g. of p-chlorobenzenethiol in 5 ml. pyridine, 960 mg. of methyl xanthide was added in one portion. Evaporation of excess pyridine and volatile byproduct gave the known bis(p-chlorophenyl) disulfide in quantitative yield (1.4 g.). No free thiol could be detected by titration with iodine. The product was easily recrystallized from ethanol. Similar results were obtained using ethyl instead of methyl xanthide.
EXAMPLE 2
A solution of 1.4 g. of p-chlorobenzenethiol in 9 ml. of pyridine was treated with 3 g. of starch xanthide containing 23 percent sulfur. After standing for 10 min., 15 ml. of acetone was added and the mixture was filtered. Evaporation of excess solvents gave 1355 mg. of bis(p-chlorophenyl) disulfide.
EXAMPLE 3
A solution of 2 g. of benzenethiol in 2 ml. of pyridine was treated with 2 g. of methyl xanthide. Evaporation of solvents gave the phenyl disulfide in quantitative yield. The reaction was somewhat slower when the experiment was repeated under similar conditions but using only 100 mg. of pyridine.
EXAMPLE 4
One gram of benzenethiol was mixed with 1 g. of methyl xanthide and treated with 70 mg. of triethylamine. On standing for a few minutes, the phenyl disulfide crystallized out quantitively. Similar results were obtained when the triethylamine was replaced with 50 mg. 5N sodium hydroxide.
EXAMPLE 5
One gram of 3-mercaptopropionic acid in 5 ml. of pyridine was mixed with 1 g. methyl xanthide. Evaporation of excess solvent gave the known propionic acid disulfide in quantitative yield. The product was easily recrystallized from water.
EXAMPLE 6
A solution of 1.2 g. of 4-mercaptophenol in 5 ml. pyridine was treated with 1 g. of methyl xanthide. In evaporation of solvents the corresponding known phenol disulfide (1.1 g.) was obtained which was crystallized from a mixture of ligroin-benzene.
EXAMPLE 7
A solution of 350 mg. of cysteine in 0.5 ml. of water was mixed with 214 mg. of methyl xanthide and 0.5 ml. of pyridine. The corresponding disulfide, cystine, precipitated almost immediately from the solution. After dilution with 10 ml. of water, the mixture was filtered and cystine was dried to yield 200 mg.
EXAMPLE 8
A solution of 1.55 g. of ethane dithiol was mixed with 3.52 g. methyl xanthide and 3 ml. of pyridine. Evaporation of the pyridine gave 1.2 g. of acetone insoluble polymeric disulfide with m.p. 130°-150° .
EXAMPLE 9
To a solution of cysteine hydrochloride (1.75 g.) in ethanol (5.0 ml.) were added methyl xanthide (1.07 g.) and pyridine (0.5 g.). Immediately, a white precipitate formed. The mixture was stirred for 1 min., kept for 5 min., and filtered. The solid was washed with ethanol (10 ml.) and acetone (10 ml.) and dried. Yield of cystine was 1.09 g., 89 percent, m.p. decomposed 260°; S, 26.5 percent (theory, 26.7 percent). | A simple and selective technique for the oxidation of thiols resulted in high yields of the corresponding disulfides. The reaction is tailored so that all byproducts are either volatile or insoluble and the end product recovered easily in essentially pure form.
A nonexclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of U.S. Ser. No. 09/999,551, filed Oct. 24, 2001 (Attorney Docket No. AGLE0049), all of which is incorporated herein in their entirety by this reference thereto.
FIELD OF INVENTION
[0002] This invention relates generally to speech recognition technology, and more specifically to a system and method for speech-activated navigation.
BACKGROUND OF THE INVENTION
[0003] Speech recognition system has been in development for more than 25 years resulting in a variety of hardware and software tools for personal computers. Products and services employing speech recognition are developing rapidly and are continuously applied to new markets.
[0004] With the sophistication of speech recognition technologies, networking technologies, and telecommunication technologies, a multifunctional speech-activated communications system, which incorporates TV program service, video on demand (VOD) service, and Internet service and the like, becomes possible.
[0005] This trend of integration, however, creates new technical challenges, particularly in the field of navigating or browsing via a speech control interface.
[0006] For example, when the system is in the Internet browsing mode, the user could feel disappointed if the system is not responsive to a spoken command which is not very well matched with a button label displayed on a Web page. Therefore, a mechanism for extending speech-activated navigation to another available search engine in certain circumstances is desired.
[0007] Another example of technical challenge is that, when the system is in a video on demand (VOD) mode, traditional method of navigating hierarchical menus will no longer meet the efficiency needs. Hierarchical menus are widely used in automated systems that permit users to pick a desired item from a large list. The list for instance could be a list of items for sale, a list of films that may be vended by a video on demand (VOD) system, or some other kind of list.
[0008] The use of a hierarchy allows a user to reach a final selection by making a small number of choices among alternatives, perhaps a sequence of three to five such choices, where each intermediate choice narrows the range of list items from which the final selection will be made. For instance, in a video on demand (VOD) system, the range of selections in principle consists of every movie ever filmed, which of course may be a very long list. But if the selection process advances by indicating first a genre, then an actor, and so on, the long list may be navigated quickly. For this reason, hierarchical menus are quite common in graphical user interfaces, touchtone-based interactive telephone systems, and other modes of list selection.
[0009] A key drawback of hierarchical menu systems, however, is that they can be tedious and cumbersome to use. In particular, the choices must be made in the order dictated by the designer of the hierarchical system.
[0010] What is further desired is a means for alleviating the tedium, through the automatic creation of an automatic speech recognition system and associated grammar(s) and database(s), embodying the same list of selections and selection criteria present in a given hierarchical menu system, but conducted through the medium of the spoken word, and moreover, using modes of statement that are natural and fluent, rather than simply mirroring in words the selections that might be made either with a cursor and graphical display in the case of a graphical user interface, or a telephone keypad in the case of an interactive telephone system.
[0011] Another example of technical challenge is that when the system is in a video on demand (VOD) mode, if the user did not speak exactly the button label displayed by the speech control interface or if the input utterance is lower than a pre-set confidence level, the system may fail to recognize the correct command and thus the system would be unable to provide the service that the user requested. For example, in a one-grammar-path-per-title approach, if the user spoke “American President” instead of “The American President”, the user's command would not be mapped to the correct movie “The American President”.
[0012] Therefore, a system that can more generously recognize the user's input utterance without sacrificing reliability is further desired.
SUMMARY OF THE INVENTION
[0013] In one embodiment, the invention provides an approach to extend speech-activated navigation to Internet search. The system enables speech access to the Internet by mixing fixed grammars with open vocabulary for an open query to a search engine. If the spoken request doesn't match the vocabulary defined for the Internet browser to proceed, the entire spoken request is passed to a search engine that processes it and displays the results of the search. Then, the user may navigate the open Web with a speech-activated browser.
[0014] In another embodiment, the invention provides a means for alleviating the tedium of hierarchical menu browsing, through the automatic creation of an automatic speech recognition system and associated grammar(s) and database(s), embodying the same list of selections and selection criteria present in a given hierarchical menu system, but conducted through the medium of the spoken word, and moreover using modes of expression that are natural and fluent, rather than simply mirroring in words the selections that might be made either with a cursor and graphical display (in the case of a graphical user interface), or a telephone keypad (in the case of an interactive telephone system).
[0015] In another embodiment, the invention provides a mechanism to recognize the user's input utterance using a new grammar structure and a matching score system. In case that the user exactly spoke a movie title, a grammar structure based on each single movie title is generated and the command associated with the recognized movie title is linked and the video server delivers the movie to the user. In case that the user's input utterance does not match any movie title, generated is a grammar structure based on each single word of a list of candidate movie titles that may be selected—they may be the entire movie titles available in the database or a partial list determined according to a certain criterion. The speech recognizer first recognizes the keywords from the input utterance; then it applies the recognized keywords, via the grammar structure, to the candidate movie titles; and then, a processor computes the matching score of each movie title in the list. Finally, the processor decides the movie with highest matching score as one that the user desired and maps or links this movie title to a command acceptable by the video server, which in turn delivers the movie to the user. The matching score may be computed based on various standards, including but not limited to, the number of recognized words that appear in each movie title.
BRIEF DESCRIPTION OF THE DRAWING
[0016] FIG. 1 is a block diagram of a speech-activated multifunctional communications system 100 ;
[0017] FIG. 2A is an exemplary word page 200 that appears on the screen as a collection of buttons with text on them;
[0018] FIG. 2B is a diagram illustrating a grammar structure 220 and a query process wherein an input utterance 210 matches a grammar path 201 a representing the textual content of a button 201 shown in FIG. 2A ;
[0019] FIG. 2C is a diagram illustrating a grammar structure 220 and a query process wherein an input utterance 240 does not match any grammar path and the recognized text 250 for the input utterance 240 is passed to an Internet search engine 251 ;
[0020] FIG. 3A is an exemplary page 300 of a speech control interface 107 for a speech-activated video on demand (VOD) system;
[0021] FIG. 3B is a diagram illustrating a grammar structure 320 and a query process wherein an input utterance 310 matches a grammar path 303 a representing the movie title 303 shown in FIG. 3A ;
[0022] FIG. 3C is a diagram illustrating a grammar structure 350 and a query process wherein every single word included in a list movie titles is assigned to a distinct grammar path and an input utterance 340 not exactly matching to a movie title is recognized based on a word matching score system.
DETAILED DESCRIPTION OF THE INVENTION
[0000] A. Speech-Activated Communications System
[0023] FIG. 1 is a block diagram illustrating a speech-activated communications system 100 , which provides interactive program guide (IPG) service, video on demand (VOD) service, and World-wide Web browsing (Internet) service. The system incorporates a “real world” type experience, allowing the end user to complete the process of finding, selecting, and purchasing program and movie content. For example, upon confirmation of the purchase of a movie or selection of a television program, the selected movie, program, or channel is immediately displayed on the television screen.
[0024] The communications system 100 includes a speech-activated remote control 102 , a personal computer (client) 104 , a remote server 112 , and a television set 109 . The user 101 gives spoken commands using the remote control 102 that converts acoustic signals into electromagnetic signals or other kind signals receivable by a wireless receiver. The signals are interfaced to the personal computer 104 via a serial port and a communication protocol 103 . The speech recognition system 105 running in the personal computer 104 converts the received signals into digital signals that can be executed by the personal computer. The automatic grammar generator 106 is an application for generating different grammar structures for different services. Using the remote control 102 , the user 101 may browse for service via a speech control interface 107 . The speech control interface may be in different modes depending on the service requested. For example, it is in VOD mode for video on demand (VOD) service. When an input utterance is processed, a specific grammar is applied to the speech recognition system 105 . The computer processes the output of the speech recognition system 105 and executes the commands associated by the output. The service that the user requested is then delivered by the server 112 via NTSC 111 or Ethernet 110 and rendered on TV screen 109 via NTSC 108 . The server 112 also provides Internet Proxy service 118 so that the user may browse the Internet via the speech control interface 107 .
[0025] The server 112 is coupled to one or more content databases ( 114 and 116 ) that store content items such as movies, television programs, television channels, and etc. Typically, the databases are encoded for a database manager supporting the SQL format and include a movie list, television program list, actor list, and genre format. The content from the server 112 is visible as a window within the static interface or in full-screen mode, as the speech control interface demands.
[0000] B. Open Vocabulary Enhancement of Speech Activated Internet Browsing System
[0026] One embodiment of this invention is a system for enhancing or extending a speech-controlled Web browsing within the framework of the communications system 100 described above. In order to understand the invention, it is necessary to review the design of Web pages and speech-controlled Web browsers in general. We begin with the review, and then explain the nature of the invention.
[0027] A Web browser is a program running on a computer, typically called the client. This program receives textual descriptions of displays, also known as Web pages, to create on the client computer screen from another computer, typically called the server. The textual descriptions are written in a specific computer language, called HTML. The action of the Web browser is to interpret the HTML, and thereby render onto the client computer screen the combination of graphics and text specified in any selected Web page.
[0028] Typically there are regions of the rendered screen, labeled with text, that cause the client computer to take some action when the user moves his mouse over the affected region and clicks a mouse switch. These regions are themselves called “buttons.”
[0029] The standard technique for speech-enabling a Web browser is to scan the HTML description of a page, and identify the text that is associated with each button, the text hereafter called a “button label.” The button labels are then assembled into a grammar, where each arc or pathway through the grammar corresponds to a single complete button label. For a speech-enabled Web browser, the grammar and the speech recognition system are so arranged that when a user speaks the text that is associated with a given button label, the speech recognition system causes the client computer to take the same action that it would have taken had the user activated the same region of the screen by use of the mouse. Note that by nature of the construction of the grammar, the vocabulary that can be recognized for the page consists exclusively of the words that appear within button labels.
[0030] The problem with this approach is that the system is limited to all and only the text supplied with the HTML page. This makes it impossible to direct the browser to fetch and load an arbitrary Web page.
[0031] The approach according to this invention is an augmentation of the above scheme for speech-enabled Web browsing. As described above, the speech-enabled browser attempts to recognize an input utterance using the grammar constructed from button labels. However, if no one arc through the grammar is a satisfactory match for the utterance, the system will abandon this approach. Instead, the utterance will be reprocessed by an open vocabulary recognizer which may be a sub-system of the speech recognition system. Such an open vocabulary recognizer is not constrained by a grammar, but is designed to recognize arbitrary utterances constructed from a very large vocabulary, typically 50 , 000 words or more. The output of the recognition process will then be provided as a query to a search engine, which will seek and display Web link options that are a close match to the given query.
[0032] We proceed to give greater detail on the architecture of this system. FIG. 2A shows an exemplary word Web page 200 that appears on the screen as a collection of buttons with text on them. The first button 201 corresponds to a news story that says: “Bush plans to smoke them out.” The second button 202 says: “Angelina Jolie film released; photos.” The third button 203 says: “J Jervis elected to management hall of fame.” The text in the buttons is available to us in the form of HTML. The system takes the HTML and analyzes it, and then processes it into a grammar, which in this example, has three phrases associated with it: the first is the Bush phrase; the second is the Angelina Jolie phrase; and the third one is the Jim Jervis phrase.
[0033] This grammar is then supplied to the speech recognition system 105 , which proceeds to use the grammar to recognize the utterances given as input. FIG. 2B illustrates the case in which the user speaks, for example, the first statement corresponding to the first button 201 . The grammar 220 has three grammar paths, 201 a , 202 a , and 203 a , with reference to three button labels shown in FIG. 1A . The input of the process is the user's utterance (“Bush plans to smoke them out”) 210 , which is recognized by the speech recognition system 105 as a corresponding to the text “Bush plans to smoke them out” 230 . Associated with the statement 201 a , we have an action, which is also embedded in the grammar 220 —not necessarily with square bracket 201 b . Here the bracket 201 b represents the fact that some additional information is being associated with the statement 201 a . This may be a little piece of program implementing a command to activate a link 201 c that lies underneath the button label 201 .
[0034] In the case when an utterance matches closely to an arc of the grammar, the speech recognition system 105 will simply invoke the associated action such as 201 c . However, if no arc of the grammar matches well, the system will reprocess the input utterance using an open vocabulary recognizer, and pass the resulting text to a standard Web search engine. FIG. 2C illustrates an example of this process, wherein the user's utterance 240 fails to match with any path of the grammar 220 . The system processes the utterance 240 using an open vocabulary recognizer 105 b and passes the output 250 (i.e. the recognized text) to an Internet search engine 251 . As a result of the search, a Web page is delivered and rendered 251 .
[0035] The follow steps further explains how this process works:
Taking a Web page as shown in FIG. 2A ; Scraping the Web page for its textual content; Generating a grammar 220 as shown in FIG. 2B for the textual content, and applying this grammar to the speech recognition system 105 ; Inputting an audio signal representing the user's utterance; Determining the confidence level of the recognized statement representing the audio signal against a pre-set confidence level; If the confidence level is high enough, i.e. the input utterance matches one of the grammar paths, then as FIG. 2B illustrated, executing the command associated with the recognized button label; If the confidence level is not high enough, i.e., it fails to match any of the grammar paths ( 201 a , 202 a , 203 a ) in the grammar 220 , then as FIG. 2C illustrated, passing the utterance through an open vocabulary recognizer 105 b , which is designed to transcribe arbitrary statements or texts that do not match any particular grammar; Taking the output 250 from that open vocabulary recognizer 105 b as the input to an arbitrary Internet search engine such as Alta Vista or Yahoo Search. As a result, it comes back with a number of hits of Internet link options.
[0043] In summary, if the system cannot reconcile the text on a screen button with the spoken command (i.e. the input utterance), then it just defaults the command and leads to a broad Internet search.
[0000] C. Automatic Grammar Generation from Hierarchical Menus
[0044] Another embodiment of the invention is an architecture for automatic grammar generation from hierarchical menus. The architecture consists two key elements. The first one is a database, which lists the items from which a final selection is to be made. Each item in the original list is an entry in the database. Moreover, each entry is labeled with the selection criteria that it satisfies, as expressed in the original hierarchical menu system. Consider for example a long list of titles, comprising both television shows to be aired over a given period of time, and films available from a video on demand (VOD) system. Those database entries corresponding to the first category would bear some indication that they are television shows; those entries corresponding to movies would likewise bear some indication they are movies. Note that some titles would bear both indications. Continuing with this idea, a given title might also bear some indication of which actors appear in the show or movie, who directed the work, when it was produced, and so on. Any criterion embedded in the original hierarchical menu would be mirrored by indications made in the automatically generated database.
[0045] The second key element is the means to generate one or more grammars, reflecting the different selection criteria that may be applied against the database entries. (For information on the structure and meaning of a grammar in this context, consult the document “OSR 1.0 Developer's Guide,” published by Speechworks International, 2001.) Continuing with the example, if the actors appearing in a television show or movie may be used as a selection criterion, then a grammar consisting of all actor names appearing in any database entry is generated. As we explain further below, the eventual idea is that if a given actor's name is spoken, only films or shows in which that actor appears will be extracted from the database.
[0046] The grammars for each different selection criterion are embedded within a larger grammar or set of grammars, which is constructed in such a manner that either a sequence of spoken commands (for instance, the uttering of the criterion name “actors,” followed by the actress name “Angelina Jolie”), or a fluent statement such as “show me films starring Angelina Jolie” will obtain the database entries with the desired property, in a manner identical to selection by the same criteria within the original hierarchical menu system. The result of this action can then be further refined by continuing the process in the same way, but with additional selection criteria applied, to further narrow the entries obtained from the database. For example, if the system is not sure about the exact name of the actor or actress called, it presents to the user an intermediary screen with a list of actor candidates, and the user can make further selection from the list.
[0000] D. Use of Inexact and Partial Match to Improve Accuracy of Speech Recognition
[0047] FIG. 3A illustrates an exemplary page 300 of a speech control interface for a speech-activated video on demand (VOD) system. A user may navigate through a large list of films by titles by operating various buttons on a remote control or by giving spoken commands via a microphone incorporated in the remote control. In the exemplary page 300 , each movie title is presented in a button. For example, button 301 is for “Rain Main”, button 302 for “X Files”, button 303 for “The American President”, button 304 for “American Graffiti”, and button 305 for “Ferris Bueller's Day Off”, etc.
[0048] Normally when we deal with this list of titles, the list is represented by a grammar in which each complete title corresponds to one arc or choice within the grammar. FIG. 3B illustrates such a grammar structure 320 wherein each arc represents a path for a movie title in the list shown in the Web page 300 . For example, arc 301 a is for “Rain Main”, arc 302 a for “X Files”, arc 303 a for “The American President”, arc 304 a for “American Graffiti”, and arc 305 a for “Ferris Bueller's Day Off”, etc.
[0049] The input to the speech recognition system 105 is the user's utterance 310 . The system processes the utterance 310 against the grammar 320 . The path through the grammar that matches the utterance most closely in the acoustic sense is the output of the speech recognition system. For example, when the user spoke “The American President”, the title “The American President” 303 was recognized and the speech recognition result 330 was mapped into a command 331 acceptable by a video server (See FIG. 1, 113 and 114 ).
[0050] In reality, users may garble and drop off words, for instance, saying “American President” rather than “The American President.” For that reason, the word “the” was missing here. That would cause the path 303 a to get a poor acoustic match score against the given utterance. The title “American Graffiti” 304 is not what the user said, but matches fairly well because the spoken word “American” matches “American”, and “Graffiti” in 304 is about the same length as “President” in 203 . It could end up getting a higher score than the desired film, just because the user neglected to utter the initial definite article “the” in the full title, “The American President.”
[0051] To solve this problem, we create a different grammar structure. Instead of keeping each movie title in one single path, we take all available movie titles from the database and cut each movie title into individual words such as “rain”, “man”, “the”, “X”, “files”, “American”, “graffiti”, “president”, and so on. Every single word included in any movie title is incorporated into the grammar structure as shown in FIG. 3C wherein each single word represents a single path. Moreover the grammar 350 is structured in such a way that each such word may be spoken any number of times.
[0052] In this case, when the utterance “American President” 340 is presented to the speech recognition system 105 , the word “American” is recognized, followed by the word “President”. Note that no association with the specific movie title “The American President” is yet made. The resulting sequence of words is called the keyword sequence S.
[0053] In the broadest conception of the invention, the keyword sequence S is then matched against a set of candidate titles C. Each element C i of C is then matched against S, by a function hereafter called ComputeScore(S, C i ). The elements of C are then sorted in decreasing order of quality of match. The resulting list may then be used in one of a number of ways, for example:
The single top-scoring C i may be presented as the recognizer output, or Some predetermined number k of elements of C, consisting of the top-scoring k candidates, may be presented to the user, for final selection, or All elements whose score lies within some range or fraction of the top-scoring C i may be presented to the user, for final selection.
[0057] The ComputeScore(S, C i ) function may take any one of a number of forms. We list some of the possibilities, with the understanding that this is not to limit the scope of claim of the invention: A simple definition, illustrated in FIG. 2D , is to count the number of words of S that appear in each given C i ;
A more sophisticated definition takes into account the relative order of words in S and C i , computing a higher score when the words of S and Ci are in the same order and position; This score or some variant of it may be normalized by the number of words of the given C i , so that long titles are not anomalously favored; This score or some variant of it may be normalized by the fraction of words in S that could match any word in C i , so that a candidate that matches a few words of S well is not anomalously favored over another candidate C i that matches more words, but with an error in position; and The definition may take the recognition system's confidence of each word of S into account, in counting matches.
[0062] In addition, in one variant of the invention, the candidate list C is generated dynamically from a database, where certain criteria, if activated under user control, prevent adding a given title to the candidate list.
[0063] In another variant of the invention, in the process of dynamically generating the candidate list C, the words in the list are optionally processed into a form that matches the form of words used in the grammar. By this is meant, for instance, spelling out numbers as text.
[0064] In summary, the process described above includes the following steps:
Creating a grammar structure 350 wherein every single word of each movie title that may be recognized is assigned to a distinct path in the grammar, and moreover so that any such word may be uttered any number of times and intermixed in order with any other word of the grammar; Recognizing an utterance 340 by a speech recognizer 105 a; Applying the recognized keywords of the utterance to each candidate title in a list which may be a list of the whole database entries, or a smaller list selected from the database based on a certain criterion; As indicated by the loop 351 , returning each candidate title's matching information to the processor 105 c; Computing the score of each candidate title; Mapping the movie title with highest matching score into a command 361 acceptable by a video server (See FIG. 1, 113 and 114 ).
[0071] Although the invention is described herein with reference to the preferred embodiment, one skilled in the art will readily appreciate that other applications may be substituted for those set forth herein without departing from the spirit and scope of the present invention.
[0072] Accordingly, the invention should only be limited by the claims included below. | The invention discloses a system and method for speech-activated navigating or browsing via a speech control interface used in a speech-activated multifunctional communications system. In one embodiment, the invention provides an approach to extend speech-activated navigation by linking an output of an open vocabulary recognizer to an Internet search engine in order that a user may have more options to search information related to his spoken commands. In another embodiment, the invention provides a means to enable the user to orally navigate a database via a speech control interface wherein the selections and associated selection criteria are organized into a hierarchical view menu. In another embodiment, the invention provides an approach with high flexibility and accuracy to recognize the user's command using a new grammar structure and a matching score system. | 6 |
BACKGROUND OF THE INVENTION
This invention relates generally to a method and apparatus for slicing fruits and vegetables including mushrooms. Particulary, it relates to such method and apparatus having a plurality of rotating cutter blades for slicing mushrooms that are conveyed to and through the rotating blades.
Mushroom slicing method and apparatus previously used in the industry as shown U.S. Pat. No. 2,178,920 to Savery issued Nov. 7, 1939, and U.S. Pat. No. 2,978,003 to Benekam issued Apr. 4, 1961, have encompassed sets of intermeshing rotating cutting blades set within a tank of flowing water. In Savery, the blades are mounted parallel to each other on a horizontal rotating shaft whose axis of rotation is perpendicular to the direction of water flow within the tank. Mushrooms are dumped into one end of the tank and are carried by the flow into the intermeshing vertical blades which coact to slice the mushrooms. Most mushrooms entering the blades float in an upright position with their heads up and stems down and are sliced along their vertical axes accordingly. The water current carries the emerging slices to the other end of the tank where they are removed.
In the Benekam patent, by contrast, the blades are mounted on a vertical shaft and thus are horizontal. The current carries the mushrooms into coacting sets of parallel blades which slice the upright mushrooms entering them perpendicular to their vertical axes.
A principal disadvantage of such prior mushroom slicing apparatus is that mushroom slices tend to become wedged between the blades rather than pass through them. The slices are compressed between blades, and their resiliency causes them to bind. Unless the slices are continuously removed, the spaces between the blades become clogged, impairing the effectiveness of the subsequent slicing action. Scraping the slices from between the blades and shaft is one approach, shown in U.S. Pat. No. 3,788,176 of Glass issued Jan. 29, 1974. But at least some of the mushroom slices are bruised and damaged by the force of the scraper.
Another drawback of prior mushroom slicing apparatus arises because of the intermeshing blades. These blades overlap with a fine tolerance and eventually are driven out of alignment as they slice through the mushrooms. To preserve the blades and assure optimum slicing of the mushrooms, the slicing apparatus must be shutdown regularly to realign or replace the blades.
Also in the prior devices, a significant share of mushrooms are not fed into the blades oriented for optimum slicing, i.e., parallel to the stem axis. Improperly sliced mushrooms are of a lower value and must be separated from the other slices, a time-consuming and costly process.
SUMMARY OF THE INVENTION
A primary object of the present invention is to provide an improved method and apparatus for slicing food such as mushrooms at a high rate.
Another object of the invention is to provide such a mushroom slicing method and apparatus in which the mushrooms are optimally sliced.
A further object of the invention is to provide such a slicing method and apparatus in which a single set of rotating blades accurately slices mushrooms.
Yet another object of the invention is to mount adjustably the blades for maintaining their slicing efficiency and for ease of replacement.
Still another object of the invention is to provide such a slicing method and apparatus which releases the sliced mushrooms from between slicing blades without damage.
The foregoing and other objects, features, and advantages of the invention will become more readily apparent hereinafter.
A slicing apparatus in accordance with the present invention comprises a set of spaced-apart circular blades mounted along a shaft for rotation therewith. The blades are positioned on the shaft to converge and diverge successively as they rotate about the shaft. Food pieces are sliced at a point just following the closest approach of the blades to each other, the blades thereafter diverging to facilitate the removal of the sliced pieces. Means convey the food pieces, such as mushrooms, in a preferred position to the rotating blades which engage an opposed drum to slice the pieces. The slices are further conveyed beyond the blades for collection.
In a preferred embodiment of the invention, the center section of the shaft is made of a flexible material. It is fitted to rigid extensions mounted in blocks to rotate the center section in a bowed configuration about a curved lengthwise axis of symmetry. The blades are concentrically mounted on the curved portion of the shaft, the bowing of the shaft causing them to converge as they rotate toward the inward side of the shaft and diverge as they rotate toward the outward side of the shaft.
The shaft and blades form part of a removable cutting head assembly which has swingable support arms for lifting the assembly free of the apparatus. A lever removably attached to the upper end of each arm is adjustable for positioning the assembly to maintain engagement between the blades and the drum as the edges of the blades recede from wear.
In a second embodiment, the blades are mounted in a fanned configuration on a straight shaft. Guide flanges resting on bearings are mounted outside each outermost blade to press the blades together on one side of the shaft, allowing them to diverge on the opposite side. The blades are dimensioned slidably to adjust along the rotating shaft to hold their orientation.
In each embodiment, resilient spacer means are inserted between the blades to maintain proper spacing of the blades. A stabilizing comb is preferably provided to align continuously the blades by fingers which penetrate between the blades just above the mushroom's entry point. On the opposite side of the shaft, a water cleaning comb with penetrating fingers is positioned. Water is sprayed from the ends of the fingers of the cleaning comb to wash any adhering mushroom slices from the blades and shaft.
The conveying means includes a flume through which water flows to deliver the mushrooms to the blades. After the slices are discharged from between the blades, they are carried by the stream of water onto a meshed conveyor which removes them from the apparatus. The water drains through the conveyor into a collecting tank. From there, a pump recirculates the water to the flume.
Within the flume, an inclined conveyor means submerges the mushrooms to a predetermined depth. When released, the mushrooms orient themselves with their caps up and stems down as they float toward the surface of the water and enter the blades in this desired position.
The present invention offers a significant improvement in the slicing of mushrooms. The mushrooms are oriented in the preferred slicing position. The circular blades mounted on the shaft diverge after the slicing to break the adhesion of the slices to the blades and allow the majority to fall away. The penetrating spray from the cleaning comb removes those slices that remain. The opposing drum with annular grooves guides the blades, increasing the accuracy of slicing operation. The slicing with a single set of blades engaging the drum avoids the need for frequent adjustment and realignment required of intermeshing blades.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a top view of a mushroom slicing apparatus in accordance with the preferred embodiment of the invention
FIG. 2 is a side view taken along the line 2--2 of FIG. 1;
FIG. 3 is a schematic view in section of the apparatus taken along the line 3--3 of FIG. 1;
FIG. 4 is an enlarged, fragmentary sectional view taken along the line 4--4 of FIG. 1 showing the details of the mounting of the cutter head assembly, the latter being shown in phantom in slicing position with the underlying drum;
FIG. 5 an enlarged sectional view taken along line 5--5 of FIG. 1;
FIG. 6 is a fragmentary top view of the cutter head assembly and drum with cutter head raised to its removal position;
FIG. 7 is a fragmentary sectional view of the cutter head assembly taken along the line 7--7 of FIG. 4;
FIG. 8 is an enlarged fragmentary view of the shaft and a pair of blades showing the arrangement for maintaining spacing between blades;
FIG. 9 is a fragmentary view taken along line 9--9 of FIG. 5 showing the cleaning comb;
FIG. 10 is an enlarged sectional view taken along line 10--10 of FIG. 9;
FIG. 11 is a sectional view of the cleaning comb taken along line 11--11 of FIG. 10;
FIG. 12 is a view taken along line 12--12 of FIG. 5 showing the stabilizing comb; and
FIG. 13 is a top view partly in section of a second embodiment of the invention comprising blades positioned on a straight shaft.
DETAILED DESCRIPTION
A Preferred Embodiment
Referring to FIGS. 1-3, a mushroom slicing apparatus 12 according to the preferred embodiment includes an inlet flume 16 through which water 20 flows from an infeed end 22 to carry mushrooms 24 to a set of rotating circular slicing blades 26 which bear against an anvil roll or drum 28. The mushrooms to be sliced are fed at a continuous even rate to the flume 16 by suitable means, indicated herein as comprising a belt conveyor 30. The water flows through the blades 26, carrying the mushrooms slices into a receiving flume 18 and onto an discharge conveyor 32 which preferably is an endless metal mesh belt 33 that retains the slices while allowing the conveying water to drain through into a tank 36. A pump 40 recirculates the water flow from the tank 36 back to the flume 16 through a pipe 42.
Means are provided in the flume 16 to submerge the mushrooms carried therein. The illustrated means comprises an inclined conveyor 44. The conveyor 44 has an inlet end 46 positioned above the water in the flume and an outlet end 48 positioned in a depressed tank-like part 49 of the flume about 18 inches below the surface of the water. The conveyor comprises a belt 50 extending the width of the flume and having a plurality of longitudinally spaced conveyor flights 52 attached thereto. The belt 50 is trained around suitable drive rollers 54, 56 driven by a motor 57 to propel the belt 50 in a counterclockwise direction as viewed in FIG. 3. Whole mushrooms carried by the water 20 into the spaces between flights 52 are propelled by the conveyor 44 to its bottom end 48. There, the mushrooms are released and allowed to float upward. Because of the greater buoyancy of the enlarged head of the mushroom, it tends to orient itself head up as it floats upwardly toward the surface of the water. A submersive depth of about 18 inches is sufficient to permit almost all the mushrooms to assume this preferred orientation. Immediately upstream from where the mushrooms break the surface, a nozzle 38 is positioned to maintain the flow of water through the flume 16. The water flow carries the mushrooms toward the cutting blades 26.
Because of the orientation attained in the flume, the mushrooms are sliced by the blades 26 along planes extending generally parallel to the axis of the mushroom stems. Without this process of submerging and releasing the mushrooms from under water, many of the mushrooms would enter the blades 26 in various positions indicated in FIG. 3 in the infeed end 22 of the flume and be sliced accordingly.
Means are provided to mount the blades 26 to cause their peripheries to converge and diverge successively as the blades rotate. Referring to FIGS. 4-7, the cutting blades 26 are mounted concentrically on the center section 70 of a curved or bowed shaft 72 positioned over the spill end 74 of the flume 16. The shaft section 70 is composed of flexible resilient material such as polyurethane, such that it can rotate about a curved axis of symmetry 76 lying in a plane indicated in FIG. 4 by the dotted line 77 inclined at an angle of about 60° to the vertical and approximately tangential to the surface of the drum 28. Each end of the section 70 is fitted into a cylindrical cup 68 forming one end of a rigid metal shaft extension 78. The shaft extensions are each rotatably supported in a pair of pillow blocks 80, 82 rigidly mounted on suitable support brackets 84 at the respective sides of the apparatus. The support brackets are adjustably mounted to support plates 83 to adjust the angle of the extensions 78 toward each other and thereby the extent of bow in the shaft center section 70. The shaft 72 is driven at each end by synchronized motors 85 mounted to reducers 86 bolted to the outer ends of each support bracket 84.
With the shaft so mounted, the center section 70 deforms to allow the shaft axis of symmetry 76 to maintain its curved orientation. The flexible material expands on the outward side 87 of the section 70 and compresses on the inward side 88.
The blades 26 are mounted on the shaft section 70 in parallel, evenly spaced relation while the shaft is dismounted from its supporting pillow blocks 80, 82, as will be described. However, the curve of the shaft in its mounted position causes the blade to converge on the inward side 88 of the curve and fan apart on the outward side 87 of the curve, as best seen in FIG. 7. The spacing between adjacent blades 26 may, for example, vary from 0.200 inch between the cutting edges of the blades at the narrowest point on the inward side 88 of the shaft to a spacing of 0.260 inch at the their greatest spacing on the outward side 87 of the shaft.
As more clearly seen in FIGS. 5 and 8, between each pair of blades 26 is mounted an intervening spacer 92 to maintain the separation of the blades. Each spacer 92 comprises a spacing disc 94 of a rigid material such as polycarbonate with an inner hub 95 and an outer ring 97 of stainless steel. The disc 94 has a plurality of equiangularly spaced holes therethrough. In each of the holes is mounted a resilient spacer member 96 which protrudes outwardly from the opposite side surfaces of the disc and into contact with the adjacent cutting blades. The resilient members 96 press against and guide the blades to prevent their wobbling while they rotationally converge and diverge. The members 96 may be of any suitable resilient material and preferably comprise rubber balls. They compress as the blades converge on the inward side 88 of the shaft and expand to urge the blades apart on the outward side 87 of the shaft.
Referring to FIGS. 6 and 7, the assembly of the cutting blades 26 and the spacers 92 is retained in position on the shaft 70 by a pair of metal guide flanges 98, one mounted outside each outermost cutting blade and held in position by a cylindrical stainless steel adjustment bushing 100. Each bushing is adjustably threaded into position on the outside of the cylindrical cup end 68 of each shaft extension 78 to press the flanges 98 firmly against the blades 26. One end of the bushing 100 is formed as a notched collar 102 through which a set screw 101 extends. Tightening the screw locks the bushing in position on the cup 68.
The blades 26, spacers 92, and guide flanges 98 are frictionally secured to the section shaft 70 in their retained position by a binding fit resulting from the out-of-round deformation of the section in its mounted position. In its dismounted position, the center section is straight, with a diameter a few mils less than the inner diameter of the blades, spacers, and flanges. They are slipped onto the shaft and positioned by adjusting the bushings 100. Upon bending the shaft 70 for mounting it in the pillow blocks 80, 82, the resulting out-of-round deformation widens the shaft relative to the mounted blades, spacers, and flanges, binding them in place to rotate with the shaft.
Referring to FIGS. 4 and 6, the blades 26 and shaft 72 form part of a removable cutter head assembly 104 which can be removed from the machine for sharpening or replacing the blades. FIG. 4 shows the assembly in its slicing position within the frame. FIG. 6 shows a top view of the assembly in its elevated position for facilitating replacement of the blades. The assembly can also be adjustably positioned to maintain contact between the blades 26 and drum 28. The cutter head assembly 104 includes a tubular member or bridge 106 which extends across the frame above the blades 26. The bridge 106 is supported at each end by tubular support members 108 fixed to the support plates 83. The support plates 83 rest upon support blocks 110 fixed to the apparatus frame at each side thereof. Welded to the inner side of each support member 108 is one of a pair of support arms 114 which extend angularly upwardly from the member 108 in the operative position of the apparatus. Each of the arms 114 is removably connected at its upper end by a pivot pin 116 and cotter keys 118 to an arm 120 of an L-shaped lever 122. The levers 122 are pivotally mounted onto the sides of the flume on stationary bearing plates 124. Stops 126 welded to each arm 120 bear against each support arm 114 when the levers 122 are pivoted clockwise, as viewed in FIG. 5, to move the assembly 104 upwardly. The other arm 128 of each lever is welded to a crossbar 130 to the middle of which is welded a jack bearing 132. A threaded spindle 134 extends through the jack bearing and threadedly engages a threaded jack bracket 136 secured to the machine frame.
Turning the spindle 134 so as to cause it to withdraw from the jack bracket 136 causes the bearing 132 and attached lever arms 128 to move upwardly, pivoting the levers 122 counterclockwise. The support arms 114 move to the left, causing the support plates 83 and attached blade assembly to slide across the blocks 110 toward the drum. The cutting blades 26 can thus be maintained in proper position to the suface of the drum 28 by adjusting the spindle 134.
To replace the blades, the cutter head assembly 104 is elevated to swing the blades free of the apparatus frame. The spindle 134 is first rotated to pivot the levers 122 clockwise. The stops 126 rotate clockwise to urge the support arms 114 upwardly, pivoting the assembly 104 upwardly and away from the drum 28, as shown in FIG. 6. Removing the pivot pins 116 and cotter keys 118 from the support arms allows the assembly 104 to be lifted free from the machine and replaced.
The anvil drum 28 is mounted below the cutter head assembly at the discharge end of the flume 16 so that the water 20 flows over the drum. As shown in FIG. 7, the curve of the shaft section 70 causes the edges of the cutting blades 26 to intersect the plane 77 along an arc concentric with the curve of shaft section 70. The drum 28 has a surface layer 140 preferably of bronze such as polyurethane, the surface of which layer is convexly curved longitudinally of the drum complementary to the curvature of the adjacent edges of the cutting blades 26. The surface layer is also formed with a series of slits 142 into which the blades 26 project. The drum 28 is mounted on a shaft 144 rotatably supported on the apparatus frame in suitable bearing mounts 146 driven by a motor 148 so that the drum rotates counter to the rotation of the cutting blades 26 at substantially identical peripheral speed.
Referring now to FIG. 5, the water flowing through the flume 16 is maintained at such height that the mushrooms float with their heads up and stems down above the flume bottom as they approach the cutting blades 26. The flow rate in the flume is preferably maintained so that the blades imbed sufficiently into the impinging mushrooms to carry them down onto the drum 28 where the blades slice entirely through the mushrooms. The shaft 72 is preferably oriented with respect to the drum so that the point of maximum convergence 152 of the blades lies above the drum at the approximate level of impingement by the oncoming mushrooms. With this orientation, the blades spread apart as the slicing is completed at a drum engagement point 154 and continue to spread apart to a point of maximum divergence 156 diametrically opposite the convergence point. The spreading of the blades breaks the adhesion of the mushroom slices to the faces of the blades and allows them to fall from between the blades into the receiving flume 18.
To facilitate and assure removal of the mushroom slices that fail freely to fall from between the blades, means are provided to wash the slices from between the blades. Referring to FIG. 5 and particularly to FIGS. 9-11, the illustrated means comprises a hydraulic cleaning comb 160 mounted on the bridge 106. The comb includes a hollow body portion 161 defining a manifold 162 and hollow fingers 163 which extend one between each pair of blades. The fingers are each formed with openings 164, see FIGS. 10 and 11, to project jets of water 165 downwardly between each blade. The body portion 161 is secured to the bridge 106 by bolts 166 with an intervening gasket 167. The manifold 162 communicates with the interior of the bridge 106 through aligned openings in the bridge, gasket and comb body indicated at 167', 167", and 167'", respectively, in FIG. 10. Water is pumped into the comb 160 from the tank 36 by the pump 40 through a pipe 168 (FIG. 3), connected to an inlet 169 to the bridge 106. The water jets 165 from the openings 164 spray along the faces of the blades 26 and against the shaft 72 to remove mushroom slices which have adhered to the blades and shaft, causing them to fall into the receiving flume 18. The removal of the slices is facilitated because of the greater spacing between the blades 26 at the finger's location.
Additional means for stabilizing the blades 26 is shown in FIGS. 5 and 12. Mounted to the apparatus frame over the drum 28 is a stabilizing comb 170. The comb has a body 172 extending the width of the blade assembly and a plurality of guide fingers 174 extending one between each adjacent pair of blades. The fingers are spaced to maintain the blades in uniform alignment as they rotate downwardly toward the mushrooms for slicing.
As indicated earlier, the sliced mushrooms are removed from the apparatus for further processing by the discharge conveyor 32, driven in the clockwise direction viewed from FIG. 3 by conventional means (not shown).
Referring to the schematic of FIG. 3, the water flowing into tank 36 is recirculated by the pump 40 to several points in the apparatus 12. The pipe 42 delivers water to the infeed end 22 of flume 16 to provide the water current for carrying the mushrooms fed into the flume towards the conveyor 44. The pipe 168 delivers water to the cleaning comb 160. A third pipe 176 delivers water to the nozzle 38.
Operation
In operation of the preferred embodiment, whole mushrooms are fed into the infeed end of flume 16 from the conveyor 30 as shown in FIGS. 2 and 3. The water current in the flume carries them toward the conveyor 44, which causes them to be submerged to the bottom of the flume 16. Upon release, they float upward to the surface with the heads above the stems in the preferred position. The surface current carries the desirably oriented mushrooms toward the slicing blades 26 and drum 28.
The mushrooms impinge upon the blades 26 and are sliced by the action of the blades and the drum 28. The blades 26 spread as they slice through the mushrooms, breaking the adhesion of the slices to the blade faces. The water current from the inlet flume 16 carries most of the slices over the drum 28 into the receiving flume 18. Those slices that remain are washed from the blades 26 and the shaft 72 by the water jets 165 emitted from the cleaning comb 160.
The current carries the slices down the receiving flume toward the discharge conveyor 32 by which they are transported to a discharge point 180 as the water drains through the conveyor into the tank 36. From the tank, the pump 40 recirculates the water throughout the apparatus 12.
Second Embodiment
This embodiment illustrates an arrangement for mounting a plurality of blades 26' on a straight, rigid shaft 72' so that the blades successively converge and diverge as they rotate with the shaft.
Referring to FIG. 13, the circular blades 26' are mounted on a rigid, straight shaft 72' between opposing angularly disposed circular guide plates 182. Each end of the shaft is rotatably supported in a pillow block 184 and driven by a motor 186 through a gearbox 188. As in the first embodiment, spacers 92' provided with resilient members 96' are mounted one between each pair of blades 26' uniformly to space the blades. The blades, spacers, and guide plates have inner diameters slightly larger than the diameter of the shaft, allowing them to slide adjustably along the shaft. A key 190 running longitudinally the length of the shaft 72' matingly engages corresponding key notches (not shown) in the blades 26', the spacers 92', and guide plates 182 to prevent slippage of this whole assembly as it rotates and adjusts.
A pair of bearings 192 mounted on the ends of angularly disposed stationary brackets 194 press against the outside of each guide plate 182. Each bracket 194 is welded to an adjustment bushing 100' which is threaded to an externally threaded bushing 185 fixed to and extending from the mounting brackets 196 for the pillow blocks 184 and gearboxes 188. The brackets are angled inward on the side of the shaft 72' towards the drum 28'. The interaction of the brackets 194 bearing against guide plates 182 and the spacers 92' with the blades 26' causes the blade edges to converge as they rotate toward the drum 28'. As they rotate away from the drum, the resilient members 96' urge the blades apart. During their rotation, the blades, spacers, and guide plates slide back and forth along the shaft 72' as necessary to adjust to their relationship.
Mounting the blades between guide plates on a straight shaft, as above described, is a simpler and less expensive manner for effecting the desired change of blade relationship as the shaft rotates. However, this embodiment is practical only over a relatively small cutting width, approximately 61/2 inches. By contrast, blades mounted on the curved shaft can be effective over a greater cutting width for a greater rate of slicing and hence better productivity.
Other means for positioning the blades to converge and diverge successively as they rotate with the shaft include the placement of stationary guides between each set of adjacent blades. These means, however, are merely other embodiments of the present inventon, differing only in form.
Having illustrated and described the principles of my invention, it should be apparent to those persons skilled in the art that the preferred embodiment may be modified without departing from such principles. I claim as my invention all such modifications as come within the spirit and scope of the following claims. | A food slicing method and apparatus includes blades mounted on a shaft for rotation therewith, the blades successively converging and diverging to slice the food pieces as the shaft rotates. An inlet flume conveys the food pieces to and through the rotating blades. A flighted conveyor within the flume submerges the food pieces at the flume inlet and releases them at the bottom of the flume to float upward, oriented according to their buoyancy before entering the blades. In one embodiment, the blades are mounted on a curved shaft which rotates about a longitudinal axis of symmetry to cause the blades to converge on the inward side of the shaft and diverge on the outward side. The blades engage a synchronously counterrotating drum to slice the food pieces as they enter on the inward side of the shaft. As the blades diverge, the majority of the slices fall free of the blades. Those that adhere are discharged from between the blades by jets of water sprayed from a water cleaning comb on the outward side of the shaft. In a second embodiment, the blades are mounted on a straight rotating shaft. Guide plates on the ends of the shaft angle toward each other to press the blades inward on one side of the shaft. The blades slidably adjust on the shaft as it rotates to converge on the one side and diverge on the other side. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to processes for producing a salt of N-guanidino thiourea and 3-amino-5-mercapto-1,2,4-triazole, which are useful as intermediate materials for medicines and pesticides. More specifically, it relates to a process for a salt of N-guanidino thiourea (i.e., "GTU salt"), which is an intermediate for 3-amino-5-mercapto-1,2,4-triazole (i.e., "ASTA"), by reacting, while heating, (i) a compound having both a thiocyanate group and an aminoguanidino group, or (ii) (a) a compound having a thiocyanate group and (b) a compound having an aminoguanidino group, in the presence of an acid, while heating, in a polar solvent. Furthermore, the resultant GTU salt can be converted to ASTA by heating the same under alkaline conditions.
2. Description of the Related Art
Several processes for producing ASTA are already known in the art. For example, DE-A-1960981 proposes a process for producing ASTA by dissolving aminoguanidine bicarbonate in ethanol containing acetic acid dissolved therein, followed by charging gaseous carbon disulfide thereto, after adding triethylamine, as follows. ##STR1##
However, this process has the problems that the carbon disulfide reagent is toxic, flammable and explosive, and therefore, the production plant becomes expensive because special precautions must be taken in the apparatus (for example, the use of closed or sealed apparatus and the installation of means for treatment of exhaust gases and waste water, etc.).
U.S.S.R. Patent No. 1002291 proposes the synthesis of ASTA by reacting aminoguanidine hydrochloride and thiourea in a molten state in the absence of a solvent as follows. ##STR2##
However, this process also has the problems that the reaction yield is not satisfactory. In addition, the starting thiourea is said to be toxic and carcinogenic, and therefore, the production plant becomes expensive.
Further, JP-A-59-124333 discloses a process for producing ASTA by reacting, while heating, GTU hydrochloric salt by dissolving the same in an aqueous sodium hydroxide. However, this publication does not disclose a method for preparing GTU. Furthermore, the present inventors proposed in JP-A-5-247004 the preparation of ASTA is prepared by reacting, in the absence of a solvent, aminoguanidine thiocyanate, or a salt of aminoguanidine and a salt of thiocyanic acid. However, this process still has the problems that the reaction rate and yield are not commercially satisfactory.
SUMMARY OF THE INVENTION
Accordingly, the objects of the present invention are to eliminate the above-mentioned problems of the conventional processes and to provide a novel process for industrially producing GTU salts and ASTA at a high yield and at a low cost.
Other objects and advantages of the present invention will be apparent from the following description.
In accordance with the present invention, there is provided a process for producing a salt of N-guanidino thiourea comprising the step of allowing to react (i) a compound having both a thiocyanate group and an aminoguanidino group, or (ii) (a) a compound having a thiocyanate group and (b) a compound having an aminoguanidino group, in the presence of an acid while heating in a polar solvent.
In accordance with the present invention, there is also provided a process for producing 3-amino-5-mercapto-1,2,4-triazole comprising the steps of
(1) allowing to react (i) a compound having both a thiocyanate group and an aminoguanidino group, or (ii) (a) a compound having a thlocyanate group and (b) a compound having an aminoguanidino group, in the presence of an acid while heating in a polar solvent, to thereby form a reaction mixture containing a salt of N-guanidino thiourea; and
(2) allowing to react the resultant reaction mixture in the step (1) under alkaline conditions, while heating.
In accordance with the present invention, there is further provided a process for producing a salt of N-guanidino thiourea comprising the steps of:
(1) allowing to react hydrazine and cyanamide in the presence of acid in a polar solvent, while heating to thereby obtain aminoguanidine;
(2) allowing to react the resultant aminoguanidine with a salt of thiocyanic acid in the presence of an acid in a polar solvent, while heating.
In accordance with the present invention, there is further provided a process for producing 3-amino-5-mercapto-1,2,4-triazole comprising the steps of:
(1) allowing to react hydrazine and cyanamide in the presence of an acid in a polar solvent., while heating to thereby obtain aminoguanidine;
(2) allowing to react the resultant aminoguanidine with a salt of thiocyanic acid in the presence of an acid in a polar solvent, while heating, to thereby form a salt of N-guanidino thiourea; and further
(3) allowing to react the resultant salt of N-guanidino thiourea under alkaline conditions, while heating.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will be better understood from the description set forth below with reference to the accompanying drawings, wherein:
FIG. 1 is an IR spectrum of the hydrochloric acid of N-guanidino thiourea obtained in Example 1, which is an intermediate of 3-amino-5-mercapto-1,2,4-triazole; and
FIG. 2 is an IR spectrum of 3-amino-5-mercapto-1,2,4-triazole obtained in Example 2.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will now be described in more detail.
In the first step reaction for producing GTU salts, (i) compounds having both a thiocyanate group and an aminoguanidino group, or (ii) (a) compounds having a thiocyanate group and (b) compounds having an aminoguanidino group, are allowed to react in the presence of an acid, while heating, in a polar solvent.
Typical examples of a compound having both a thiocyanate group and an aminoguanidino group are aminoguanidine thiocyanate. Examples of a compound having a thiocyanate group, usable in the present invention, are ammonium thiocyanate, potassium thiocyanate, sodium thiocyanate, lithium thiocyanate, calcium thiocyanate, magnesium thiocyanate, barium thiocyanate. Among these, the use of ammonium isothiocyanate is industrially preferable because of its good process operability and easy availability.
Examples of a compound having an aminoguanidino group, usable in the present invention, are aminoguanidine hydrochloride, aminoguanidine sulfate, aminoguanidine nitrate, aminoguanidine bicarbonate, and aminoguanidine hydrobromide. Among these, the use of aminoguanidine bicarbonate is industrially preferable because of its good processability and easy availability.
When ammonium thiocyanate is used as the compound having a thiocyanate group, for example, and aminoguanidinobicarboxylic acid is used as the compound having an aminoguanidino compound for example, these compounds can be first reacted while heating in a polar solvent in the absence of an acid to obtain aminoguanidine thiocyanate by, for example, distilling off the formed ammonia and carbon dioxide, together with water, and the resultant aminoguanidine thiocyanate can be allowed to react in the presence of an acid, as desired.
The acids usable in the first step of the present invention are not specifically limited and preferably include inorganic acids such as hydrochloric acid, sulfuric acid nitric acid, phosphoric acid, etc. These can be used alone or in any mixture thereof. The use of hydrochloric acid or sulfuric acid is preferable because of their good reactivity and easy availability.
The polar solvents usable in the present invention preferably include, for example, water and lower aliphatic alcohols having 1 to 3 carbon atoms, such as, for example, methyl alcohol, ethyl alcohol, iso-propyl alcohol. The use of water is most preferable.
The first step reaction of the present invention is considered to proceed as shown in the following reaction (1) or (2): ##STR3##
In the reactions (1) and (2), X represents a residual group of the acid.
As is clear from the above-reaction schemes (1) and (2), one equivalent of the thiocyanate group and one equivalent of the acid are necessary, based upon one equivalent of the guanidine group. Nevertheless, from the viewpoints of the desirable reactivity, the use of, preferably 1 to 5 equivalents, more preferably 1 to 2 equivalents, of the thiocyanate group and the use of, preferably 1 to 10 equivalents, more preferably 1 to 3 equivalents, most preferably 1 to 2 equivalents, of the acid are desirable, both based upon 1 equivalent of the guanidine group.
The acid can be used in any manner, and the manner of using the acid is not specifically limited. If necessary, the acid can be added to the reaction system by diluting with water to an appropriate concentration.
The reaction is generally carried out at a temperature of 50° C. or more, preferably at a temperature of 80° C. to 120° C. from the viewpoints of the reaction rate, the decomposition of the starting materials and the resultant GTU and the suppression of side reactions.
Although there are no specific limitations to the reaction time, the preferable reaction time is 5 minutes to 4 hours, preferably 10 minutes to 3 hours.
After the reaction is terminated, the resultant reaction mixture is optionally concentrated and cooled to precipitate the GTU salt, which is the intermediate the desired compound ASTA according to the present invention, followed by filtering. Thus, the crystal of the desired GTU salt can be obtained. Since the GTU salt has a certain water-solubility, a considerable amount of the GTU salt is dissolved in the filtrate. However, when the filtrate is recycled, the yield of the GTU salt can be improved.
The type of the salt of the GTU salt depends on the acid used in the first step reaction, and therefore, the examples thereof are the salt of the above-mentioned inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid and phosphoric acid. The preferable salts are the hydrochloride and sulfate, especially the hydrochloride.
In the second step of the present invention, the desired compound ASTA can be produced by dissolving the GTU salt obtained in the above-mentioned manner in the polar solvent as mentioned above, then making the resultant GTU solution alkaline by adding, for example, an alkaline compound, followed by reacting under heating. Alternatively, the reaction mixture obtained in the above-mentioned first step reaction can be directly used, without separating the salt of GTU after completing the first step reaction, as the starting GTU solution for the second step reaction.
The second step reaction of the present invention is considered to proceed as in the following reactions (3) and (4): ##STR4## wherein M represents a univalent metal and X represents a residual group of the acid. ##STR5##
Examples of the above-mentioned alkaline compounds are hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide and lithium hydroxide.
As the method for using the alkali compounds, it is preferable that the alkali compounds can be dropwise added to the reaction system by diluting the same to an appropriate concentration with, for example, water. The pH of the reaction mixture is preferably 7 to 14, more preferably 9 to 13.
Although there are no specific limitations to the reaction time, the reaction time is preferably 10 minutes to 6 hours, more preferably 1 to 2 hours.
After the reaction is completed, the desired ASTA can be obtained at a high purity by adjusting the pH of the resultant: reaction mixture with an above-exemplified acid such as hydrochloric acid. When a further purified product is desired, the resultant product can be purified by, for example, column chromatography or acidlysis (or acid precipitation).
As the acidlysis, the resultant ASTA obtained as mentioned above is first dissolved in an aqueous solution of an alkali metal hydroxide (e.g., sodium hydroxide) to form an aqueous solution of an alkali metal salt of ASTA. The insoluble impurities such as sulfur are separated by filtration under vacuum, followed by drying to obtain the desired ASTA crystal at a 85-100% purity.
In accordance with the other embodiment of the present invention, the desired GTU salts and ASTA can be produced from hydrazine and cyanamide, both of which are easily available at an industrial scale.
That is, the GTU salt can be produced by reacting hydrazine (usually hydrate) and cyanamide in the presence of an acid in a polar solvent, while heating to thereby obtain aminoguanidine, followed by reacting the resultant aminoguanidine with a salt of thiocyanic acids in the presence of an acid in a polar solvent, while heating (e.g., 50° C. to reflux temperature), as shown in the following reactions (5), (6) and (7). ##STR6## wherein X represents a residual group of the acid and M represents a metal ion or ammonium ion.
The acids, polar solvents and salts of thiocyanic acids usable in the above reactions are the same as those mentioned above. Although there are no limitations on the amounts of the acid and cyanamide, 0.9 to 1.5 mol of the acid and 1.0 to 1.5 mol of the cyanamide are preferably used in the reaction based upon 1 mol of the hydrazine. The preferable reaction time is 0.5 to 12 hours. The GTU salt can be recovered in the same manner as mentioned above.
According to the present invention, the aminoguanidine obtained in the reaction (6) can be directly reacted, without first recovering the same, or it can be first separated from the above reaction mixture, and then reacted, with thiocyanate to form GTU salt.
The GTU salt obtained above can be directly, or after separating, reacted to the desired ASTA, in the same manner as mentioned above.
Examples
The present invention will now be further illustrated by, but is by no means limited to, the following Examples.
Example 1
To a 100 ml flask provided with a thermometer and an agitating means, 27.2 g (about 0.2 mol) of aminoguanidine bicarbonate, 15.2 g (about 0.2 mol) of ammonium thiocyanate, and 10 g of deionized water were charged. The mixture was heated in an oil bath until the temperature of the reaction mixture became 108° C., whereby the water, carbon dioxide and ammonia were distilled off.
Then, a reflux condenser was attached to the reaction flask. While the reaction mixture was heated to 95° C. while stirring, 28.0 g (about 0.27 mol) of 35% by weight hydrochloric acid was dropwise added over two hours, after which the temperature was maintained for one more hour. Thereafter, the reaction mixture was cooled to room temperature and the precipitated crystal was recovered by filtration. The wet crystal thus obtained was dried at 50° C. under a reduced pressure overnight. Thus, 16.3 g (about 0.11 mol) of the desired GTU hydrochloride crystal having a 91% purity was obtained. The melting point of the resultant GTU hydrochloride was 195°-197° C. Furthermore, its infrared (IR) spectrum is shown in FIG. 1. In addition, 9.3 g (about 0.07 mol) of the GTU hydrochloride was still dissolved in the filtrate, and therefore, the total yield of the GTU hydrochloride, together with the recovered crystal, was about 95% based upon the aminoguanidine bicarbonate.
Example 2
Aminoguanidine bicarbonate, ammonium thiocyanate and deionized water were added to the same flask as used in Example 1 in the same amounts as in Example 1. The reaction mixture was heated in an oil bath in a similar manner as in Example 1 to distill off water, carbon dioxide and ammonia. Then, a reflux condenser was attached to the reaction flask and the reaction mixture was heated at 95° C. and 28.0 g (about 0.27 mol) of 35% hydrochloric acid solution was dropwise added over 2 hours, while heating and stirring as in Example 1. After the dropwise addition of the hydrochloric acid, the reaction mixture was allowed to stand at the same temperature for 1 hour to obtain the reaction mixture containing the GTU hydrochloride.
Then, to the reaction mixture, 18.3 g (about 0.23 mol) of 50% by weight aqueous solution sodium hydroxide solution was added to make the reaction mixture alkaline, and the mixture was reacted while refluxing (at about 110° C.) for 1.5 hours on an oil bath. After the completion of the reaction, the reaction mixture was cooled to room temperature, followed by adding 9.5 g of 35 wt % hydrochloric acid to adjust the reaction mixture to a pH of 1 to 2. The resultant precipitate of ASTA thus obtained was filtered to obtain 24.5 g of water-containing ASTA. The water-containing ASTA thus produced was dried at 50° C. under a reduced pressure overnight to obtain 19.2 g of the ASTA crystal having a purity of 97.1% (i.e., about 0.161 mol, yield of about 80.3% based on aminoguanidine bicarbonate). The decomposition temperature of the resultant ASTA was 298°-301° C., and its IR spectrum is shown in FIG. 2, and is approximately the same as that of the standard sample.
Example 3
The production step of the reaction mixture containing the GTU hydrochloride in Example 2 was repeated except that 13.2 g (about 0.13 mol) of 98 wt % conc. sulfuric acid was used instead of 28.0 g (about 0.27 mol) of 35 wt % hydrochloric acid. Thus, 16.8 g of ASTA crystal (i.e., 0.138 mol, 70.5% yield based on the aminoguanidine bicarbonate) was obtained. The decomposition temperature thereof was 295°-299° C., which was substantially the same as that of the standard sample.
Example 4
To a 5 liter separable flask provided with a thermometer and an agitating means, 1382 g (about 10 mol) of aminoguanidine bicarbonate, 767 g (about 10 mol) of ammonium thiocyanate and 500 g of deionized water were charged and the mixture was heated in an oil bath and water, carbon dioxide and ammonia were distilled off until the reaction temperature reached 108° C.
Then, a reflux condenser was attached to the reaction flask, and the reaction mixture was heated at 95° C., while stirring, and 1247 g (about 12 mol) of 35 wt % hydrochloric acid was dropwise added over 2 hours. The reaction was further maintained at the same temperature for one hour to obtain the reaction mixture containing the GTU hydrochloride.
To the resultant reaction mixture, 650 g (about 6.5 mol) of 40 wt % aqueous sodium hydroxide solution was then added to adjust the reaction mixture to an alkaline condition and the mixture was allowed to react in an oil bath under reflux (about 110° C.) for 1.5 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, followed by adding 383 g of 35 wt % hydrochloric acid to adjust the pH thereof to 1-2. The resultant ASTA precipitate was separated by filtration to obtain 1296 g of the water-containing ASTA. The water-containing ASTA was dried at 50° C. under a reduced pressure overnight to obtain 935 g (about 7.71 mol, about 77.1% yield based on aminoguanidine bicarbonate). The decomposition temperature of the resultant ASTA was 295°-297° C. and the result of IR analysis was the same as shown in FIG. 2, both of which are substantially the same as those of the standard sample.
Example 5
To a 500 ml flask provided with a thermometer, a reflux condenser and an agitating means, 51.2 g (0.505 mol) of hydrazine hydrate (H 2 NNH 2 .H 2 O) and 46.7 g (0.46 mol) of 36 wt % hydrochloric acid were charged and the mixture was mixed while maintaining the temperature at 40° C., followed by adding 44.8 g (0.532 mol) of cyanamide thereto. The mixture was heated to 90° C. for 4 hours. Thus 51.8 g (93.8% yield, based on hydrazine hydrate) of aminoguanidine hydrochloride (AGH) was obtained.
To the reaction mixture obtained in the first step reaction above, 53.4 g (0.70 mol) of ammonium thiocyanate (NH 4 SCN) was added and, by dropwise adding 71.6 g (0.706 mol) of 36 wt % hydrochloric acid thereto, the temperature of the reaction mixture was raised to allow to react while refluxing (at about 105° C.), followed by aging at 100° C. for 3 more hours. Thus, 71.5 g (84.4% yield) of N-guanidino thiourea hydrochloride was obtained.
To the reaction mixture obtained in the second step, 125 g (1.25 mol) of 40 wt % aqueous sodium hydroxide solution was carefully added and the mixture was reacted at a pH of 10.4 while refluxing (at about 105° C.) for 4 hours. The reaction mixture thus obtained was allowed to cool to about 30° C. (pH =8.0), followed by dropwise adding 80.2 g (0.79 mol) of 36 wt % hydrochloric acid to adjust the pH thereof to 0.9. Thus, the precipitate of the desired ASTA was obtained.
The resultant precipitate of the crude ASTA was separated by filtration to obtain 55.3 g (0.37 mol, 73.5% yield, based on hydrazin hydrate) of the water-containing ASTA. The water-containing ASTA thus prepared was dissolved in 100 g of 20 wt % aqueous sodium hydroxide solution (pH=11.5), followed by filtration and washing with water. To the resultant filtrate, 50.6 g of 36 wt % hydrochloric acid was added to adjust the pH of the mixture to 5.9, followed by heating while refluxing at (105° C.) for 2 hours. The mixture was cooled to 25° C., 51.0 g of the purified ASTA thus obtained was dried at 80° C. under a pressure of 80 Torr overnight. Thus, 38.7 g (purity 99.5%, 0.33 mol, 66.4% yield based on hydrazine hydrate) of the purified ASTA was obtained. The decomposition temperature thereof was 297° to 300° C. and its IR spectrum is the same as that shown in FIG. 2, and both of these spectra are the same as that of a standard sample.
As explained above, according to the present invention, a salt of N-guanidino thiourea can be obtained from (i) a compound having both a thiocyanate group and an aminoguanidino group, or (ii) (a) a compound having a thiocyanate group and (b) a compound having an aminoguanidino group, none of which has been used in the prior art, in the presence of an acid, while heating, in a polar solvent, unlike the prior art processes.
Furthermore, according to the present invention, ASTA can be produced from (i) a compound having both a thiocyanate group and an aminoguanidino group, or (ii) (a) a compound having a thiocyanate group and (b) a compound having an aminoguanidino group, in the presence of an acid under heating in a polar solvent, followed by heating the resultant reaction mixture obtained above under alkaline conditions.
Furthermore, according to the present invention, the GTU salt and ASTA can be produced from hydrazine and cyanamide.
According to the present invention, the problems encountered in the prior art processes, namely the toxicity and the other dangerous properties of the starting materials and the cost increase due to the use of the various additional apparatus accompanied therewith as well as the unsatisfactory reaction yield can be advantageously solved and the desired compounds can be safely and inexpensively produced at an industrial scale. | A method for producing 3-amino-5-mercapto-1,2,4-triazole, useful as an intermediate compound for a medicine or pesticide, or the intermediate thereof, a salt of N-guanidino thiourea from aminoguanidine thiocyanate or a thiocyanate and an aminoguanidine compound in the presence of an acid in a polar solvent, or even from hydrazine and cyanamide is disclosed. | 2 |
FIELD OF THE INVENTION
[0001] The field of the invention relates to medical devices, and more particularly to an neurovascular intervention device.
BACKGROUND OF THE INVENTION
[0002] Intraluminal, intracavity, intravascular, and intracardiac treatments and diagnosis of medical conditions utilizing minimally invasive procedures are effective tools in many areas of medical practice. These procedures are typically performed using diagnostic and interventional catheters that are inserted percutaneously into the arterial network and traversed through the vascular system to the site of interest. The diagnostic catheter may have imaging capability, typically an ultrasound imaging device, which is used to locate and diagnose a diseased portion of the body, such as a stenosed region of an artery. For example, U.S. Pat. No. 5,368,035, issued to Hamm et al., the disclosure of which is incorporated herein by reference, describes a catheter having an intravascular ultrasound imaging transducer.
[0003] Currently, there exists no indicated intravascular imaging method for the neurovasculature. When evaluating a proposed intravascular imaging device for the neurovasculature, the procedure steps for coronary interventions serve as baseline. Typically, for cardiovascular intervention, the use of the imaging device alternates with the use of the treatment device, i.e., a clinician would insert the imaging device to diagnose the area of interest, and then remove the imaging device to insert the appropriate treatment device. Applied to the neurovascular system this may be particularly undesirable due to time considerations in the treatment of strokes and/or intravascular aneurysms. In such cases, it may be desirable to provide simultaneous and/or real-time intra-lumen imaging of a patient's vasculature.
[0004] In the case of a stroke caused by embolus, it may be beneficial for the clinician to determine the nature of the embolus in order to plan necessary intervention. The embolus may come in two forms, hard plaque or soft thrombus, and different treatments may be used for each. For soft thrombus, drug treatment may be preferred, since it is a more conservative treatment, but such a treatment may be ineffective for hard plaque, which may require more aggressive treatments such as stent placement. The ability to make a quick assessment benefits the patient by receiving the most applicable intervention as soon as possible.
[0005] In the case of an aneurysm, the ability to characterize the aneurysm accurately is very important, particularly for embolic coiling procedures. The diameter of the neck of the aneurysm, the diameter of the aneurysm itself, the density of the sac thrombus, and the patency of the parent artery are all important items of data when planning intervention. The ability to determine and/or confirm these items of data real time may provide a factor of safety when planning the required intervention. For example, the embolic coils originally chosen for treatment based on angiograms may have to be modified based on findings that the aneurysm neck is larger or smaller than anticipated. Accordingly, an improved intravascular intervention device would be desirable.
SUMMARY OF THE INVENTION
[0006] The present invention generally relates to medical devices, and more particularly to an improved intravascular intervention device. In one embodiment, an intravascular intervention device includes a microcatheter configured for intravascular delivery, an imaging wire received within the microcatheter, and a treatment device received within the microcatheter, wherein the imaging wire and the treatment device may be simultaneously advanced. The treatment device is configured to perform intravascular intervention. For example, the treatment device may be configured to deliver a stent, an embolic coil and/or a thrombolytic agent. In this embodiment, the intravascular intervention device may image the area of interest while performing the intravascular intervention, thus allowing imaging to take place in real time.
[0007] 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
[0008] In order to better appreciate how the above-recited and other advantages and objects of the present inventions are obtained, a more particular description of the invention briefly described above will be rendered by reference to specific embodiments thereof, which are illustrated in the accompanying drawings. It should be noted that the components in the figures are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the invention. Moreover, in the figures, like reference numerals designate corresponding parts throughout the different views. However, like parts do not always have like reference numerals. Moreover, all illustrations are intended to convey concepts, where relative sizes, shapes and other detailed attributes may be illustrated schematically rather than literally or precisely.
[0009] FIG. 1 a is a cross-sectional side view of a microcatheter in accordance with a preferred embodiment of the present invention.
[0010] FIG. 1 b is a cross-sectional view of a microcatheter in accordance with a preferred embodiment of the present invention.
[0011] FIG. 1 c is a cross-sectional view of a microcatheter in accordance with a preferred embodiment of the present invention.
[0012] FIG. 2 a is a cross-sectional side view of an imaging wire in accordance with a preferred embodiment of the present invention.
[0013] FIG. 2 b is a cross-sectional view of an imaging wire in accordance with a preferred embodiment of the present invention.
[0014] FIG. 3 is a cross-sectional view of an imaging wire in accordance with a preferred embodiment of the present invention.
[0015] FIG. 4 is a diagram of a medical imaging system in accordance with a preferred embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0016] As described above, an intravascular intervention device that allows the simultaneous delivery of an imaging device and a treatment device may be desirable. Turning to FIG. 1 a , a microcatheter 100 is shown. The microcatheter 100 is constructed to allow navigation into cerebral arteries. Such a microcatheter 100 has a size range of up to 0.027 inches. An example of such a microcatheter is described in U.S. Pat. No. 4,739,768 to Engelson, which is hereby incorporated by reference in its entirety. The microcatheter 100 includes an outer sheath 110 having a lumen that is capable of receiving an imaging wire 120 and a treatment device 150 . The microcatheter 100 may utilize a guidewire (not shown) to facilitate in advancing the microcatheter 100 to the area of interest. One of ordinary skill in the art will appreciate that both the imaging wire 120 and the treatment device 150 may be capable of being advanced beyond the distal end of the sheath 110 of the microcatheter 100 .
[0017] Turning to FIG. 1 b , which shows a cross-section of a microcatheter 100 , the microcatheter 100 may receive the imaging wire 120 and the treatment device 150 via a single lumen 103 . Alternatively, turning to FIG. 1 c, which shows a cross-section of an alternative microcatheter 100 , the microcatheter 100 may receive the imaging wire 120 and the treatment device 150 through a first lumen 102 and a second lumen 104 respectively.
[0018] Turning to back to FIG. 1 a, the imaging wire 120 includes a sheath 121 , preferably braided polymer, that is coupled with a floppy tip 124 at the distal end of the sheath 121 . The sheath 121 includes a lumen that receives an imaging transducer assembly 130 shown in FIG. 2 a . The imaging wire sheath 121 may be coated with a lubricious coating that enables improved movement within a vessel. The imaging sheath 121 preferably includes a puncture hole 122 towards the distal portion of the imaging wire 120 , which allows blood pressure to fill the cavity around the imaging element 130 to improve imaging. The sheath braid may discontinue for a particular amount of length, thus allowing the imaging transducer to acquire an image with reduced interference. The sheath 121 may be withdrawn completely after reaching the desired position, thus leaving the imaging transducer assembly 130 and the floppy tip 124 exposed to the area of interest. In such a configuration, it may be desirable to coat the assembly 130 with a lubricious and/or thrombolytic agent, such as heparin.
[0019] In an alternative configuration, the sheath 121 may be a thick walled hypotube or partially hollowed rod to allow attachment of the floppy tip 124 and passage of the imaging transducer assembly 130 . In addition, the sheath 121 may include conductive traces that allow the imaging transducer assembly 130 to be electrically coupled with a proximal connector 200 (shown in FIG. 3 ). A thin coating of insulating material may protect the conductive traces.
[0020] The floppy tip 124 may be composed of a layered coil atop a cylindrical wire that is flattened into a ribbon under the coil. Further, the floppy tip 124 may have a proximally extended axial section over which the imaging transducer 130 may translate (not shown).
[0021] Turning to FIG. 2 a, an example of an imaging transducer assembly 130 is shown within the sheath 121 of the imaging wire 120 . The imaging transducer 130 includes a coaxial cable 132 , having a center conductor wire 136 and an outer shield wire 134 , shown in FIG. 2 b. A conductive wire, having a diameter of approximately 500 microns, is wrapped around the coaxial cable 132 , forming a coil, which functions as a drive shaft 138 . The wire may be a laser cut Nitinol tube, which allows for torquability and flexibility. Alternatively, the drive shaft 138 may be composed of coaxial cables wound such that the cables are kept separated, via individual shielding or additional wire, while surrounding a neutral core. Further, the drive shaft 138 may be pre-tensioned.
[0022] Connected to the distal end of the drive shaft 138 is a stainless steel housing 140 , which serves to reinforce the structure of the imaging transducer assembly 130 . Surrounding the coaxial cable 132 , within the housing 140 is a silver epoxy 142 , a conductive material. Thus, the housing 140 is electrically coupled to the shield wire 134 of the coaxial cable 132 via the epoxy 142 . On the distal end of the silver epoxy 142 is an insulating substance, e.g., a non-conductive epoxy 144 .
[0023] Alternatively, or in addition to the configuration above, the drive shaft 138 may be printed with one or more conductive traces that allow communication between the imaging transducer 130 and a proximal connector 200 (shown in FIG. 3 ), which allows the imaging transducer 130 to connect to external circuitry 300 that processes signals, such as imaging and navigational signals, from the imaging transducer 130 , such circuits being well known (shown in FIG. 4 ). In yet another alternative configuration, the drive shaft 138 may be composed of an extruded polymer reinforced with a polymer/fiber/metal braid with the coaxial cable 132 extruded within the walls (not shown).
[0024] On the distal end of the non-conductive epoxy 144 is a layer of piezoelectric crystal (“PZT”) 147 , “sandwiched” between a conductive acoustic lens 146 and a conductive backing material 148 , formed from an acoustically absorbent material (e.g., an epoxy substrate having tungsten particles). The acoustic lens 146 is electrically coupled with the center conductor wire 136 of the coaxial cable 132 via a connector 145 that is insulated from the silver epoxy 142 and the backing material 148 by the non-conductive epoxy 144 . The acoustic lens 146 may be non-circular and/or have a convex surface. The backing material 148 is connected to the steel housing 140 . It is desirable for the imaging transducer assembly 130 to be surrounded by a sonolucent media. The sonolucent media may be saline. Alternatively, or in addition to, as mentioned above, the sheath 121 of the imaging wire 120 may include a puncture hole 122 to allow blood to surround the imaging transducer assembly 130 as well. As one of ordinary skill in the art may appreciate, the imaging transducer assembly 130 may be translatable relative to the floppy tip 124 . Further, the floppy tip 124 may be detachable, thereby exposing the imaging transducer assembly 130 .
[0025] During operation, the PZT layer 147 is electrically excited by both the backing material 148 and the acoustic lens 146 . The backing material 148 receives its charge from the shield wire 134 of the coaxial cable 132 via the silver epoxy 142 and the steel housing 140 , and the acoustic lens 146 , which may also be silver epoxy, receives its charge from the center conductor wire 136 of the coaxial cable 132 via the connector 145 , which may be silver epoxy as well.
[0026] In an alternative embodiment, transducer 130 is replaced by a phased array as disclosed in Griffith et al., U.S. Pat. No. 4,841,977, which is hereby incorporated by reference in its entirety. Further, other imaging devices may be used, instead of, or in addition to imaging transducers, such as light based apparatuses for obtaining images through optical coherence tomography (OCT). Image acquisition using OCT is described in Huang et al., “Optical Coherence Tomography,” Science, 254, Nov. 22, 1991, pp 1178-1181, which is hereby incorporated by reference in its entirety. A type of OCT imaging device, called an optical coherence domain reflectometer (OCDR) is disclosed in Swanson U.S. Pat. No. 5,321,501, which is incorporated herein by reference. The OCDR is capable of electronically performing two- and three-dimensional image scans over an extended longitudinal or depth range with sharp focus and high resolution and sensitivity over the range.
[0027] Turning to the treatment device 150 shown in FIG. 1 a, the treatment device 150 delivers treatment to an intravascular area, such as an area with an aneurysm or an embolism. One of ordinary skill in the art may appreciate that the treatment device 150 may deliver drugs, agents, or medical devices such as embolic coils or stents. U.S. Pat. No. 4,994,069 to Ritchart, entitled “Vaso-Occlusion Coil and Method,” the entirety of which is hereby incorporated by reference, describes a treatment device that delivers one or more vaso-occlusive coils.
[0028] In the foregoing specification, the invention has been described with reference to specific embodiments thereof. It will, however, be evident that various modifications and changes may be made thereto without departing from the broader spirit and scope of the invention. For example, the reader is to understand that the specific ordering and combination of process actions described herein is merely illustrative, and the invention can be performed using different or additional process actions, or a different combination or ordering of process actions. As a further example, each feature of one embodiment can be mixed and matched with other features shown in other embodiments. Additionally and obviously, features may be added or subtracted as desired. Accordingly, the invention is not to be restricted except in light of the attached claims and their equivalents. | The present invention generally relates to medical devices, and more particularly to an improved intravascular intervention device. In one embodiment, an intravascular intervention device includes a microcatheter configured for intravascular delivery, an imaging wire received within the microcatheter, and a treatment device received within the microcatheter, wherein the imaging wire and the treatment device may be simultaneously advanced. The treatment device is configured to perform intravascular intervention. For example, the treatment device may be configured to deliver a stent, an embolic coil and/or a thrombolytic agent. In this embodiment, the intravascular intervention device may image the area of interest while performing the intravascular intervention, thus allowing imaging to take place in real time. | 0 |
CROSS-REFERENCE TO RELATED APPLICATION
This application claims the benefit of European Patent Application No. filed 26 Feb. 2008, which is assigned to the assignee of the present application, and the teachings of which are hereby incorporated by reference in their entirety.
BACKGROUND
The present invention relates to the field of networked applications and, more specifically, to federation of composite applications.
FIG. 1 (Prior Art) shows an overview of the components that build up the prior art application infrastructure (AI) 11 and system architecture within an overall portal system 10 . The application infrastructure includes templating application infrastructure (TAI) 13 , composite application infrastructure (CAI) 15 , component registry 27 , and portal handler 29 .
TAI 13 can handle the templates in the system and the creation of new composite applications. CAI 15 can handle the application instances 19 during runtime and can manage connections and the data flow between the components of an application. The component registry 27 can manage the business components installed in the system. The portal handler 29 can be a specific local component that manages any portal related artifacts 8 , such as pages and/or portlets for the application infrastructure in the portal. The portal handler 29 can be used by the instantiation component 17 to create such artifacts during the creation of a new composite application.
As shown, TAI component 13 manages the templates 23 in the system which contains references to instantiable components in a local list of components 27 . As an example, a template for shopping applications can consist of a reference to a document library component which is used to hold the available goods and their descriptions, a shop portlet that lets clients process actual shopping transactions, an invoice business component that handles the payment process, and a blogging component that allows clients to comment on their satisfaction.
The TAI component 13 also creates application instances from templates via an instantiation component 17 , which creates separate instances of the referenced business components, typically by creating or copying individual configurations for these components such that multiple application instances can be created from the same template without interfering with each other.
For the above mentioned sample template, the instantiation 17 can, among other things, create an individual storage compartment in the document library, an individual configuration of the invoice component referring to the bank account, and an individual configuration for the shop portlet. The configuration for the shop portlet can be set up to display goods from the created document library and can be used to delegate payment processing to the created invoice component instance.
In particular, the instantiation 17 creates the necessary portal artifacts such as pages that allow users to interact with the created composite application. This is typically done by employing a specific handler 29 that creates portal artifacts 8 and links them with the business components of the application.
The created composite application instances 19 hold a context 25 that lists the component instances that make up the composite application.
FIG. 2 (Prior Art) shows an overview of the storage components involved in the portal architecture 10 that comprises deployment related code in a deployment component 14 and a runtime environment in one or more runtime containers 12 where the deployed components are executed. For the composite application context deployed artifacts can include application components stored in a component registry 18 and/or templates stored in a template catalog 20 . This data can be referenced by the application's instance specific data 16 .
Prior art composite applications are a key concept of the prior art “Service Oriented Architecture” (SOA). They allow end-users to assemble business logic out of a set of given components without programming by simply defining some meta information, such as configuration data and application structure.
Prior art composite applications are supported for example by the prior art IBM WEBSPHERE PORTAL and other known products.
A key element in supporting any desired services oriented architecture is giving business analysts the ability to implement complex logic using pre-built components. The components can be assembled to a coherent “composite application”, which can be developed, deployed, managed, and used as a single entity, rather than managing the included components individually.
Prior art composite applications are executed in a runtime container, which adds capabilities, such as management of application specific access control, templating, communities, roles, and the like.
While servlet/portlet containers in prior art focus on individual components and how they render User Interface (UI) information, the composite application container is adding management capabilities in prior art. This concept is, for instance, introduced by the prior art IBM WEBSPHERE PORTAL.
One conceptual disadvantageous limitation which exists is that all components need to be executed on the same server and in the same application runtime container. This disadvantage requires all components to be used within a composite application to be installed on one and the same local server system. If remote information is needed, a local “proxy” business component needs to be written and integrated in the application. The prior art proxy component imports such remote information by implementing Web services. For example, a request is sent to a remotely installed application, which receives and processes the request and sends back a response which is processed by a control container of the composite application.
A prior art composite application consists of independent components which are set together to build a union which performs some predefined business tasks as a whole. Disadvantageously, all components need to be installed at one and the same application server.
With reference to FIG. 3 (Prior Art) showing a prior art system architecture for prior art use of composite applications, a complex composite application can span multiple systems, denoted as 32 , 34 and 36 , for example a system A having a portal composite application infrastructure 31 , system B 34 being a Systems Applications and Products (SAP) system, and system C being for example a DOMINO server system, for example for an application of LOTUS NOTES. In each of the shown systems 32 , 34 and 36 a plurality of components are installed, symbolized by the puzzle-like parts in each system, wherein each component runs in its own runtime container.
According to this prior art there is no possibility to virtually execute the components in a single composite application runtime environment. Instead, programmers need inevitably to write “gluecode” for the business components which connect the various systems and the interaction of the components. This can be an error-prone work, which is additionally quite complicated and requires much programming knowledge, in particular knowledge about Systems A, B, C runtime environments. This gluecode forms a remote access, for example, from System A to System B and System C in order to cooperate and communicate with the components implemented there. The mainly used implementation is based on Web requests or on remote procedure calls.
BRIEF SUMMARY
A predetermined business task of a composite application can be fulfilled. The composite application can be a set of components. The composite application is instantiated by a template means and a predefined collaborative context module controls the interaction of the set of components during the runtime of the composite application. A set of components fulfilling individual services on individual different server systems is generated. During the runtime of the components, the interaction of the different components is controlled on individual different server systems utilizing a primary context module. The primary context module communicates with an appropriate collaborative module implemented locally on the respective set of servers, where the local context modules act as secondary context modules in relation to the primary context modules. For each of the secondary context modules, local components communicate to control the interaction of components.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 (Prior Art) shows an overview of components of a prior art application infrastructure.
FIG. 2 (Prior Art) shows an overview of the storage components involved in a portal architecture.
FIG. 3 (Prior Art) is a schematic diagram illustrating a high level system view reduced to the components of a prior art portal environment.
FIG. 4 is a depiction of a computing system illustrating an embodiment of the present invention.
FIG. 5 is an interaction diagram illustrating the basic steps of an embodiment of the present invention occurring during an instantiation of a composite application.
FIG. 6 illustrates basic steps during runtime of the composite application in accordance with an embodiment of the inventive arrangements disclosed herein.
FIG. 7 is a schematic depiction of the basic contents of a mapping table used by a central controller component controlling the interaction in accordance with an embodiment of the inventive arrangements disclosed herein.
DETAILED DESCRIPTION
The term “composite application” can define an application hosted on a Web portal platform which is built by combining and connecting multiple components such as portlets, wikis, document libraries, and Web services, for a particular purpose such as a shop or a virtual team room application. A single portal platform can host multiple instances of the same composite application, for example different team rooms for different associated user communities. Composite applications are built from a template describing the contained components, configuration, and interconnection.
An embodiment of the disclosure provides a solution to virtualize a set of different runtime environments, and to provide a centralized control component on a portal application server, which coordinates the interaction between different systems and different components installed on respective systems, in order to generate a single composite application which spans across the before mentioned multiple server systems and runtime environments.
Thus, a composite application is defined which is able to span across different server systems. As such, components from these different server systems (for example portal server systems) can be integrated into a single composite application. Properties of “points of variability”, templating, application roles, and the like can be available for this new type of composite application, which spans different server systems.
In one embodiment, external components, which may require their own runtime environment, can be advantageously used for this new type of integrated composite application. By this, it is possible to integrate different programming worlds into the new type of composite application without knowing the details of each programming world. The central control component implements all interface logic in order to handle the control of incoming and outgoing data.
When non-homogeneous runtime environments and respective components are integrated into one composite application, this composite application has a far more extended scope of functionality, because virtually all functionality existing on these different systems can be imported into the composite application.
In one embodiment, multiple systems can all have the same runtime environment and host the same type of applications. The composite application can perform load balancing tasks using these different systems. This aspect is, for example, very useful when the composite applications offer a user interface for using broadband media libraries, where a single user request triggers a relatively high network load. When a large set of such user requests must be processed, the load can be adequately distributed and thus balanced amongst the different available separate systems.
The term “components” which is used to describe programmatic resources on the different separate server computer systems is to be understood basically as a program component fulfilling a relatively clear and simple business task, for example processing emails. It should be noted, however, that the disclosed technique is also capable by means of the same features to extend this definition to also include program components having a larger functional scope, such as for example to include not only processing of emails, but also processing of contacts, calendar function, to-do-schedules, and the like.
The present disclosure addresses a problem that occurs when a composite application is desired to integrate different programming “worlds”. Such is the situation when a single composite application uses for example a Systems Applications and Products (SAP) component, running on a SAP server, further uses a media library, which streams media data, and uses finally a database intensively which is basically implemented on a third server by using a third different programming environment. In the disclosure, a composite application can integrate multiple applications running each in their own, original runtime environment.
With general reference to the Figures and with special reference now to FIG. 4 , a new virtual container denoted with reference 40 is given according to this embodiment of the invention, which comprises a federate composite application infrastructure symbolized by frame 44 and also referred to as “primary context module” 44 . This virtual container 40 implements and performs control of all interaction required between the components as they are denoted with the same reference signs as given in FIG. 3 .
According to the principal aspect of the present invention a single, virtual composite application infrastructure is provided which spans multiple systems 32 , 34 36 , as shown in FIG. 4 , wherein individual components can be executed within their native environment on which they are deployed. When the components run individually on separate systems, they are managed as part of a single composite application. As such, they do not need to be contacted by a Web request as it is done in prior art. Instead they are accessed—see arrows 42 —through a “virtual” composite application infrastructure layer, comprised of control components 33 , 35 , 37 , also referred to in here and implemented as “collaborative context modules” or “secondary context module” implemented locally on a respective system.
This virtual environment exposed functionality which is featured by the application and its components such as adding a member, setting a preference, reading data, displaying information and the like. The environment maps that functionality transparent to the user of the composite application to the components and to the appropriate individual system, on which that component is deployed. This can be done by remote procedure calls, Web services, Service Oriented Architecture (SOA)/Service Component Architecture (SCA) protocols, Web Services for Remote Portlets (WSRP) protocols, and the like.
The virtual environment 40 supports the management and configuration, as well as the interaction of the components as they are described already with reference to FIG. 3 , here however, across the different systems, without the need of developing the above mentioned gluecode or without the need to write individual business components. The components can leverage features provided by the composite application infrastructure, such as parameterizations, application roles, or template instantiation immediately.
In the depicted example of FIG. 4 , the virtual composite application environment 40 spans thus a portal system 32 , a DOMINO system 36 and a SAP system 34 .
With further reference to FIG. 5 the interaction between the depicted components is described during the instantiation of the composite application in accordance with an embodiment of the disclosed invention.
In FIG. 5 , an instantiation request for an application instance is sent to the master container. This container infrastructure triggers component instance creation requests for each of the different system environments. During instantiation it can be ensured that each created component can be linked to the cross-system overall application.
In more detail, a logical application infrastructure container, which is denoted by reference sign 40 in FIG. 4 receives a request for creating a composite application, which is shown by step 510 . This request can be triggered by invoking an API exposed by the templating capability of the virtual composite application infrastructure.
In a next step 520 , this container 40 triggers one or more “component instance creation” requests for each system environment. This is depicted by arrows 520 , 540 and 560 . Respective success notifications 530 , 550 , 570 , 580 are sent back to the Application Infrastructure Container.
With further reference to FIG. 6 the interaction between the depicted components is described during runtime of the composite application in accordance with an embodiment of the disclosed invention.
In FIG. 6 , normal usage of the application is performed by sending requests to the master container such as for example to render, to get members, to add data, to doBackup, to doCustomThings. These requests can be forwarded to each component. Each component can execute component specific actions, once triggered by a specific request and return data. In more detail, the logical application infrastructure container, which is denoted by reference sign 40 in FIG. 4 receives an application specific request for one of before-mentioned tasks, which is shown by step 610 .
In a next step 620 this container 40 triggers the “Forwarding” request or several of them for each system environment. This is depicted by arrows 620 , 640 and 660 . Respective application specific data are calculated by the respective application on its original system environment, and are sent back to the Application Infrastructure Container, see steps 630 , 650 , 670 , 680 . These result data are then available for the container and the primary controller, respectively.
A primary controller manages the components on the remote systems. This can be done based on a mapping table, which specifies the server location and the type of each component.
A typical application, which exploits the described capabilities and spans multiple systems, can include components to be executed for example within a SAP system, a DOMINO System and a Portal system. Each system contains some of the components, which belong to the overall application. Each component is managed by the overall application, but is executed within its native environment. The component, which retrieves data from a SAP repository can be implemented to exploit SAP Application Programming Interfaces (APIs), whereas the Portal components can be implemented to be based on the Portlet Java Specification Request 168 (JSR168) API. Domino components can use the native NOTES C/C++ APIs. Each component can expose its capabilities to the composite application infrastructure (e.g., by exposing Web services or remote procedure call).
Benefits resulting from use of multiple native environments are retained, while keep environment specific code and APIs to each individual component largely unchanged. The overall application implements the business value based generic services by consuming Web services. However, despite of loading environment specific code, the virtual composite application allows to manage all pieces (even the ones executed remotely) as one single entity, which represents the entire business application.
Additionally, components of the same composite application can span multiple systems for load balancing purposes. For instance, it is possible to offload individual portlets which consume significant computing power.
It should be noted that in applications based on prior art, composite applications and the composite application infrastructure are limited to a single environment. There is no prior art method of managing components of a single composite application, on multiple systems.
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 one embodiment, the invention is implemented in software, which includes but is not limited to firmware, resident software, microcode, and the like.
Furthermore, the invention can take the form of a computer program product accessible from a computer-usable or computer-readable medium providing program code for use by or in connection with a computer or any instruction execution system. 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 can 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, and the like) can be coupled to the system either directly or through intervening I/O controllers.
Network adapters can 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. | A predetermined business task of a composite application can be fulfilled. The composite application can include a set of components. The composite application is instantiated by a template means and a predefined collaborative context module controls the interaction of the set of components during the runtime of the composite application. A set of components fulfilling individual services on individual different server systems is leveraged by the composite application. During the instantiation of the composite application from a template, the referenced components (as types) are instantiated leading to runtime instances of these components. The interaction of the different components is controlled on individual different server systems utilizing a primary context module. The primary context module communicates with an appropriate collaborative module implemented locally on the respective set of servers, where the local context modules act as secondary context modules in relation to the primary context modules. For each of the secondary context modules, local components communicate to control the interaction of components. | 8 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation of, claims priority from, and incorporates by reference in its entirety co-pending U.S. patent application Ser. No. 13/290,165 which was filed on Nov. 7, 2011.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not Applicable.
BACKGROUND OF THE INVENTION
This invention relates to methods, compositions, and apparatuses for the monitoring and controlling of paper sheet characteristics on a creping process. As described at least in U.S. Pat. Nos. 7,691,236, 7,850,823, 5,571,382, 5,187,219, 5,179,150, 5,123,152, 4,320,582, and 3,061,944, in the tissue manufacturing process, a paper sheet is dried and creped on a heated drying cylinder, termed a Yankee or Yankee dryer. Creping is a process in which a steel, bimetallic, or ceramic blade (called a doctor blade) is impacted into the paper sheet, thus compressing the sheet in the machine direction (MD), creating a folded sheet structure. Creping breaks a large number of fiber-to-fiber bonds in the sheet, imparting the qualities of bulk, stretch, absorbency, and softness which are characteristic of tissue. The amount of adhesion provided by the coating adhesive plays a significant role in the development of these tissue properties. Often adhesive materials are used to coat the Yankee surface in order to help the wet sheet adhere to the dryer. This improves heat transfer, allowing more efficient drying of the sheet. Most importantly, these adhesives provide the required adhesion to give good creping of the dry sheet.
The Yankee coating also serves the purpose of protecting the Yankee and creping blade surfaces from excessive wear. In this role, the coating agents provide improved runability of the tissue machine. As creping doctor blades wear, they must be replaced with new ones. The process of changing blades represents a significant source of tissue machine downtime, or lost production, as creped product cannot be produced when the blade is being changed. Release agents, typically blends of hydrocarbon oils and surfactants, are used in association with the coating polymers. These agents aid in the uniform release of the tissue web at the creping blades, and also lubricate and protect the blade from excessive wear.
In the creping process as the paper sheet is removed from the dryer surface macro and micro folds are formed that appear sharper on the air side of the sheet, while these folds are more broken up and less sharp on the Yankee side. The resulting structures formed appear as repeating bars whose MD length (machine direction) tend to be shorter than the CD (cross direction) length. Property changes to the sheet as a result of the creping process include bulk, stretch, softness, and absorbency all increasing with strength decreasing. In particular, the tactile surface smoothness of the sheet is strongly linked to the crepe structures formed on the sheet. All of these properties are critical to the manufacturer for quality control, product development, and machine troubleshooting. Controllable variables impacting the crepe structure include coating chemistry, crepe ratio (Yankee speed/reel speed), sheet moisture level, and creping blade geometry and age. Other process variables such as furnish, forming dynamics, and fabric also affect the creping process, but are not as easily controlled.
Previous methods of evaluating creped sheet characteristics and surface topography are described at least in U.S. Pat. Nos. 5,654,799 and 5,730839, US Published Patent Application 2005/0004956, International Patent Application WO 2007/024858, and Published Articles: The Measurement of Surface Texture and Topography by Differential Light Scattering, E. L. Church, Wear, 57 (1979), 93-105, Tactile Properties of Tissue with Moire Interferometry, Lidnsay, J., Bieman, L., 1997 Engineering & Papermakers: Forming Bonds for Better Papermaking Conference, Oct. 6, 1997, TAPPI, Image Analysis to Quantify Crepe Structure, Archer, S., Furman, G., and W. Von Drasek, Tissue World Americas 2010 Conference, Mar. 24-26, 2010, Miami, Fla. USA, Reprint R-974.
Monitoring the crepe structure formed in the sheet provides insight on the machine running conditions and product quality. Manufacturers recognize this point and will routinely evaluate the sample by counting macro crepe structures using an ocular device with or without image storage capability. The procedure uses an oblique light source perpendicular to the CD of the sheet, and results in scattering light from the crepe structures to visually form alternating light and dark areas. The bright areas represent crepe bars and are manually counted over a unit length scale to determine the number of crepe bars per inch (CBI) or cm. Tracking the CBI number allows the manufacturer to assess product quality and machine running conditions. For example, a reduction in the CBI number could be linked to operating conditions such as an aging doctor blade or a moisture profile change affecting the sheet adhesion. Once the problem is identified, proper corrective action can be taken to restore the desired product quality.
However, unlike tensile strength, stretch, basis weight, caliper, and moisture, which are quantitative measurements, crepe bar counting is a qualitative subjective measurement. The subjectivity in manual CBI measurements results from the complex topography of the creped sheet being composed of macro and micro structures, free fiber ends, and fractured structures. As a result, CBI analysis is dependent on the technicians experience and skill to identify and interpret what is and is not a crepe bar structure. This lack of standardization and repeatability in manual CBI measurements is a limitation in using the information for process control decisions and product quality assessment.
Thus there is clear need and utility for methods, compositions, and apparatuses for the uniform consistent and accurate measurement of creped paper sheet properties. The art described in this section is not intended to constitute an admission that any patent, publication or other information referred to herein is “prior art” with respect to this invention, unless specifically designated as such. In addition, this section should not be construed to mean that a search has been made or that no other pertinent information as defined in 37 CFR §1.56(a) exists.
BRIEF SUMMARY OF THE INVENTION
At least one embodiment of the invention is directed towards a method of measuring the geometric characteristics of a crepe structure on a paper sheet. The method comprises the steps of: 1) Generating data values representing characteristics of positions on a paper sheet by repeatedly emitting at least two emission beams against each of the positions on the paper sheet and reflecting the two beams off of the positions and into a sensor constructed and arranged to absorb and measure the intensity of the reflected emission beams, 2) correcting the measured intensity of the data values by using an n th order polynomial fit, 3) performing a row-by-row smoothing operation of the corrected data values using a filter algorithm, 4) identifying positive to negative transitions within the smoothed data values, and 5) correlating the identified transitions with previously identified values known to correspond to particular geometric dimensions to determine geometric features of the crepe structure.
The emitted beam may be illuminating light. The sensor may be a digital camera coupled to a microscope. The emitted beam may be projected at an angle oblique to the machine direction. The emitted beam may be projected at an angle relative to the plane of the paper sheet. The emitted beam may be any form of radiation and/or any combination of radiations. The positions on the paper sheet may lie along a straight line extending in the machine direction. The filter algorithm may be one selected from the list consisting of FFT, Butterworth, Savitsky-Golay, and any combination thereof.
The method may further comprise the steps of determining the crepe frequency size distribution and converting this into a length scale. The method may further comprise the step of using more than one filtering algorithm and evaluating the results of the filtering algorithms to determine the characteristics of free fiber ends of the paper sheet. The method may further comprise the step of recognizing the periodicity of peaks in the measured data and using the periodicity to determine the softness of the creped paper sheet. The method may further comprise the step of recognizing the dispersion of peaks in the measured data and using the dispersion to determine the softness of the creped paper sheet. The method may further comprise the step of measuring both sides of the paper sheet, the method utilizing a shutter on each side of the paper sheet, the shutters constructed and arranged to block the impact of an emitted beam against a position on one side of the paper sheet when an emitted beam is impacting against the other side and also to alternate between which side is having the emitted light impact against it. The measured characteristics may be input into a system which has online control of at least some of the process equipment in a papermaking process, the system constructed and arranged to appropriately modify the settings of the process equipment if the measured characteristics are outside of a predetermined acceptable range to induce the further measured characteristics to conform to the predetermined acceptable range.
Additional features and advantages are described herein, and will be apparent from, the following Detailed Description.
DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates a perspective view of a crepe structure monitoring system.
FIG. 2A illustrates a magnified view of crepe structures in one area of a tissue sheet.
FIG. 2B is a graph of light intensity vs. pixel for a chosen ROI of a crepe structure.
FIG. 3A is a first graph of CSI decay curves of a tissue sample.
FIG. 3B is a second graph of CSI decay curves of a second tissue sample.
FIG. 3C is a third graph of CSI decay curves of a third tissue sample.
FIG. 4A is a first graph of marginal CSI values determined from FIG. 3A .
FIG. 4B is a second graph of marginal CSI values determined from FIG. 3B .
FIG. 4C is a third graph of marginal CSI values determined from FIG. 3C .
FIG. 5 is a graph of cumulative FFT spectra for three tissue samples.
FIG. 6 is a side view illustration of a device for evaluating CD profiles of crepe structures in tissue sheets.
FIG. 7 is a side view illustration of a system for spatially synchronized two sided monitoring of crepe structures in tissue sheets.
FIG. 8 is a perspective view of a system using multiple illumination sources.
FIG. 9 is a set of four different tissue sample images labeled A,B, C, and D used in the comparative analysis of Example 1.
FIG. 10 is a graph of cumulative FFT spectra for images in FIG. 9 .
FIG. 11 is a graph of marginal CSI values from tissue sample images in FIG. 9 .
DETAILED DESCRIPTION OF THE INVENTION
The following definitions are provided to determine how terms used in this application, and in particular how the claims, are to be construed. The organization of the definitions is for convenience only and is not intended to limit any of the definitions to any particular category.
“Bevel” or “bevel surface” as used herein refers to the portion of the blade that forms the surface between the leading edge of the blade and the trailing side of the blade and is typically the “working surface” of the blade.
“Bulk” means the inverse of the density of a tissue paper web and is commonly expressed in units of cm 3 /g. It is another important part of real and perceived performance of tissue paper webs. Enhancements in bulk generally add to the clothlike, absorbent perception. A portion of the bulk of a tissue paper web is imparted by creping.
“Crepe Structure” means the folds and seams present on a paper product that has undergone a creping process.
“Cross Machine Direction” or “CD” means the direction perpendicular to the machine direction in the same plane of the fibrous structure and/or fibrous structure product comprising the fibrous structure.
“Doctor blade” means a blade that is disposed adjacent to another piece of equipment such that the doctor blade can help remove from that piece of equipment a material that is disposed thereon. Doctor blades are commonly used in many different industries for many different purposes, such as, for example, their use to help remove material from a piece of equipment during a process. Examples of materials include, but are not limited to, tissue webs, paper webs, glue, residual buildup, pitch, and combinations thereof. Examples of equipment include, but are not limited to, drums, plates, Yankee dryers, and rolls. Doctor blades are commonly used in papermaking, nonwovens manufacture, the tobacco industry, and in printing, coating and adhesives processes. In certain instances, doctor blades are referred to by names that reflect at least one of the purposes for which the blade is being used.
“Fiber” means an elongate particulate having an apparent length greatly exceeding its apparent width. More specifically, and as used herein, fiber refers to such fibers suitable for a papermaking process.
“Highly polished” means surface that has been processed by a sequential progression from relatively rough grit to fine grit with suitable lubrication and is highly planar and substantially free of defects. Such sequential progression will be referred to herein as a “step polishing process.”
“Machine Direction” or “MD” means the direction parallel to the flow of the fibrous structure through the papermaking machine and/or product manufacturing equipment.
“Oblique Angle” means an angle between 0 degrees and less than 90 degrees.
“Paper product” means any formed, fibrous structure products, traditionally, but not necessarily, comprising cellulose fibers. In one embodiment, the paper products of the present invention include tissue-towel paper products. Non-limiting examples of tissue-towel paper products include toweling, facial tissue, bath tissue, table napkins, and the like.
“Sheet control” as used herein, refers to the lack of vibrations, turbulence, edge flipping, flutter, or weaving of the web that result in a loss of control at higher speeds.
“Softness” means the tactile sensation perceived by the consumer as he/she holds a particular product, rubs it across his/her skin, or crumples it within his/her hand. This tactile sensation is provided by a combination of several physical properties. One of the most important physical properties related to softness is generally considered by those skilled in the art to be the stiffness of the paper web from which the product is made. Stiffness, in turn, is usually considered to be directly dependent on the strength of the web.
“Strength” means the ability of the product, and its constituent webs, to maintain physical integrity and to resist tearing, bursting, and shredding under use conditions.
“Tissue paper web”, “paper web”, “web”, “paper sheet”, “tissue paper”, “tissue product”, and “paper product” are all used interchangeably and mean sheets of paper made by a process comprising the steps of forming an aqueous papermaking furnish, depositing this furnish on a foraminous surface, such as a Fourdrinier wire, and removing a portion of the water from the furnish (e.g., by gravity or vacuum-assisted drainage), forming an embryonic web, and in conventional tissue making processes transferring the embryonic web from the forming surface to a carrier fabric or felt, and then to the Yankee dryer, or directly to the Yankee dryer from the forming surface. Alternatively in standard through air drying (TAD) tissue making processes, the embryonic web may be transferred to another fabric or surface traveling at a slower speed than the forming surface. The web is then through air dried on this fabric to a dryness typically between 50 to 90%, and finally transferred to a Yankee dryer for final drying and creping, after which it is wound upon a reel.
“Water soluble” means materials that are soluble in water to at least 3%, by weight, at 25 degrees C.
In the event that the above definitions or a description stated elsewhere in this application is inconsistent with a meaning (explicit or implicit) which is commonly used, in a dictionary, or stated in a source incorporated by reference into this application, the application and the claim terms in particular are understood to be construed according to the definition or description in this application, and not according to the common definition, dictionary definition, or the definition that was incorporated by reference. In light of the above, in the event that a term can only be understood if it is construed by a dictionary, if the term is defined by the Kirk - Othmer Encyclopedia of Chemical Technology, 5th Edition, (2005), (Published by Wiley, John & Sons, Inc.) this definition shall control how the term is to be defined in the claims.
In at least one embodiment of the invention, a method determines the characteristics of a crepe structure. This method addresses the lack of standardization by using a processing methodology and apparatus to provide reliable and repeatable measurements of the sheet surface structure. In addition, the analysis provides a higher level of information compared to traditional manual CBI measurements that is helpful in developing correlations between analysis results and surface softness panel test data. Uses for the technology include quality control, product grade development, and process trouble shooting.
Referring now to FIG. 1 there is shown that in at least one embodiment the method in which a sensor device ( 101 ) and at least two emission sources ( 100 ) whose emission the sensor device is designed to detect. The emission sources ( 100 ) are oriented towards the creped structure of a paper sheet ( 102 ). Because the crepes extend roughly perpendicular to the MD the emission sources ( 100 ) emit beams at angles oblique to the CD. In at least one embodiment the emission sources ( 100 ) are also elevated above the plane of the paper sheet ( 102 ) at an angle θ. The orientation of the emission beams result in the sensor device ( 101 ) being able to resolve detailed 3 dimensional features such as crepe bars, fractured crepe bars, free fiber ends, fold depth, and fold width.
In at least one embodiment the sensor ( 101 ) is an optical sensor and/or a camera (digital or other) and the emission source ( 100 ) is a light lamp. In at least one embodiment the sensor/emission source is incandescent, LED, laser, UV, IR, and/or EM based. In at least one embodiment the sensor includes a magnification lens or is coupled to a microscope with a standardized illumination source. Image magnification is dependent on the sample, e.g., crepe bar size or frequency, and if other structural information such as embossed patterns is desired. Magnification at ˜20× with a field of view in the range of 4×6 mm is a good compromise to resolve enough detail to capture crepe structures that include crepe bars, fractured crepe bars, and free fiber ends. At lower magnification, information may be lost for smaller structures such as fractured crepe bars and free fiber ends. Higher magnification is useful in analyzing these structures, but resolving the overall crepe pattern in the sheet is lost.
In at least one embodiment illumination is made by positioning the emission sources ( 100 ) on both sides of the sample perpendicular to the CD with the same angle of incidences, as shown in FIG. 1 . Depending on the source characteristics, a collimating or expanding optical element may be needed to uniformly illuminate an area on the sheet larger than the camera field of view. Two sources are preferred because crepe structure identification is dependent on whether the sample is viewed from the crepe blade side or reel side. Using the combination of two illuminating sources on each side negates the manufacturing MD effect, thereby standardizing the measurement without prior knowledge on the sheet direction relative to the creping blade. For manually counting crepe bars, a dual light illumination method is not critical, since macro crepe bar structure lengths are not measured but rather counted over a known length scale.
The topography of a creped sheet is a complex 3-dimensional structure composed of macro and micro folds, fractured crepe structures, and free fiber ends. In addition, these structures can vary in height and spacing between one another. As a result, detecting the scattered light from the top of these structures using a shallow angle illumination source is dependent on the direction that the light is propagating. The directional dependency results from light getting blocked by neighboring structures, thereby producing a darker region in the image. Processing the image from the ROI (region of interest) intensity profile to identify a crepe structure will display a shift in the profile toward the direction of the illumination source. To illustrate this point, FIG. 1 shows a ROI intensity profile over a 2.0 mm distance collected with light sources independently illuminating the right and left sides of the sample, as well as with both light sources illuminating the sample simultaneously. With right side illumination only the profile shifts to the right because the scattered light intensity is dominant on the right side of the crepe structures. In this case, light scattering from nearby structures on the left side is attenuated or lost. Similarly, illuminating the sample only from the left side exhibits the same characteristics. Illuminating the sample simultaneously from both the left and right side captures the surface structures from both directions resulting in more detail.
Referring now to FIG. 2A there is shown an image collected using the invention. The two or more sources produce features undulating between light and dark which represent the detailed characteristics of the crepe structure. One of ordinary skill in the art would understand that the light and dark regions are merely indicators of different characteristics and any other means of noting two or more different characteristics is encompassed by this invention. The brighter regions correspond to structural features with high amplitude, e.g., the peak of a fold, on the sheet that scatter emissions from the illumination source whereas dark regions represent regions where emission penetration is poor. This variation in intensity can be used to identify and measure crepe structures on the sheet surface.
To illustrate the processing steps performed FIG. 2A shows a tissue paper image captured with a digital 8-bit camera using a 20× magnification lens system. At this magnification, the full image is approximately 6.4 mm wide (1024 pixels) by 4.85 mm high (768 pixels). The horizontal line on the image represents the ROI (region of interest) used to measure the variation in light intensity along the line with gray scale values ranging between 0 (black) to 255 (white). Variation in the light intensity along the ROI line is shown in FIG. 2B for the first 200 pixels. For manual counting of the crepe features, the high intensity values along the ROI are counted over a known length scale. The crepe frequency is then the total number of features counted divided by the length scale. The method developed here automates the procedure by identifying crepe features on each row of pixels over the entire image. This approach not only standardizes the means to identify crepe features that can be used to determine a crepe frequency (CBI) comparable to manual counting, but also gives information on the feature size distribution statistics.
In at least one embodiment automation of crepe feature identification uses the following steps:
1. Row-by-row baseline correction using an n th order polynomial fit (generally a 2 nd or 3 rd order polynomial is adequate to remove baseline curvature) to correct intensity variation of the image. The degree of baseline correction will depend on the magnification and uniformity of the illumination source incident on the sample. The baseline correction is made by taking the point-by-point difference between the ROI intensity profile and the polynomial fit. As a result, the mean of the corrected profile approaches zero, 2. Perform a row-by-row smoothing operation using a filter algorithm, e.g., FFT, Butterworth, Savitsky-Golay, etc., to reduce high frequency variations in the profile caused by noise and/or small features. Filter parameter selection is critical to distinguish between macro and micro structures. In manual crepe counting only macro structures are used. Inclusion of micro structures in the analysis will result in crepe frequency counts higher than typical manual counting. This does not mean that micro counts are not useful; it only means that filtering is needed to get results comparable with manual counting that tissue makers are familiar with, and 3. Crepe feature identification is made by tracking (left to right) along the ROI line to identify positive to negative intensity transitions. Identified adjacent transitions represent the beginning and ending point of a crepe feature. The identification points are shown by vertical markers on FIG. 2B for the first five crepe features identified along the 200 pixel ROI line and the number of pixels between the markers represents the feature size. By calibrating the imaging device with an object of known dimensions, the number of pixels defining the feature is converted to a length scale.
Steps 1-3 can be automated to perform a row-by-row analysis over the entire image to collect the number and size of each crepe structure identified. The processed results can then be displayed as a frequency (or percent frequency) size distribution plot in addition to a quantitative summary of the data set using standard descriptive statistics. Further reduction in the data can provide metrics that mill operators are accustomed to working with. For example, mills typically use crepe bars per inch (CBI) as a metric to assess operating conditions and product quality. A CBI metric from the processed image data is obtained by taking the reciprocal of the mean feature size from the distribution plot. To utilize the size distribution data more efficiently a breakdown in the distribution plot can be made by categorizing the feature size as fine, medium, coarse, and very coarse. This breakdown allows the operator to make a quick evaluation of the product quality to determine if any process changes are needed or not.
In at least one embodiment a method is used to transform the crepe frequency size distribution to a length scale or % length scale. This transformation effectively places more weight on the larger structures, thus providing a more sensitive indicator to the tactile feel of the sheet surface. For example, a higher density of large structures (structures>0.5 mm) indicates a coarser sheet compared to a sample with a lower density of large structures. Transformation to length scale is made in two steps. First, the total length of the image is determined by summing the features identified for all rows. Second, a subset of summed lengths is made for a predetermined range, e.g., the sum of features in the size range between 0.1 and 0.15 mm. The percentage is determined by dividing the summed subset of lengths by the total length. The procedure is repeated for different size ranges to form a % length scale plot as a function of the feature size. Similar to the frequency distribution, the length scales can be categorized as fine, medium, coarse, and very coarse to provide an efficient means to observe shifts between different length scale sizes and aid in process adjustment decisions.
In at least one embodiment the method compares and correlates the fine structures, e.g., free fiber ends or micro structures, on the sheet surface by evaluating the row-by-row profile data processed in steps 1-3 discussed above at different filtering conditions. For example, data filtering using the Savitsky-Golay method for a 1 st order polynomial with side points varying from 5 to 50 is used to generate a set of feature size distributions. The mean value from each distribution at a specific filter condition is then used to calculate a set of values defined as crepe structures per inch (CSI). Here the CSI value is determined using the same method as CBI. The difference being that CSI can include both macro and micro structures where CBI is specific to macro structures. Plotting the CSI values as a function of filter points produces a decay curve as in FIGS. 3A-3C for a set of three different samples with varying softness. Characteristic features of the curve shows an exponential decay starting at high CSI values for low filter (micro plus macro structures) conditions that approaches an asymptotic limit as filtering is increased (macro structures). Samples with a high density of surface structures, e.g., free fiber ends and fractured crepe structures, will exhibit a high sensitivity to changes in the filter level. Conversely samples with a low density of surface structures show less sensitivity to changes in the filter parameters. The characteristics of the curves in FIGS. 3A-3C such as maximum CSI, delta between maximum CSI and asymptotic limit, slope, etc., provide useful metrics in developing correlations with surface softness from consumer or expert panel tests. Further refinement in developing correlations with softness is possible using a combination of these characteristics with the descriptive statistics from size distribution data as well as size breakdown results.
Taking the first 1 st derivative of the decay curves shown in FIGS. 3A-3C gives the marginal CSI curves shown in FIGS. 4A-4C . Marginal CBI represents the change in the CSI value for a change in the number of points used with the Savitsky-Golay filter. Information extracted from the filter analysis, summarized in Table 1, compares the standard CSI values from the feature size distribution, the delta CSI values from the raw filter data, and the slopes from the marginal CBI plot. The samples listed are ranked from 1 to 3 based on tactile feel with 1 having the best surface softness and 3 being the worst. The additional information from the filter analysis extends the level of interpretation. For example, a large ΔCSI value is an indicator of the small feature population. Comparing differences between the standard CBI and ΔCSI values for air and Yankee sides shows the delta analysis gives a larger value. The difference is even greater for the marginal slope analysis when comparing the percent change value (percent change represents the increase in the value (CBI, ΔCSI, and Marginal slope) between air to Yankee sides) for each analysis. Therefore, the varying filter analysis provides a higher sensitivity to surface changes.
TABLE 1
Filter analysis results from samples with different softness ranking (1 = best, 3 = worst).
Softness
CBI std.
CBI std.
%
Δ CSI
Δ CSI
%
Marginal
Marginal
%
Sample
Ranking
Air
Yankee
Change
Air Side
Yankee Side
Change
Air Slope
Yankee Slope
Change
1
1
103
106
2.83
80
89
11.25
0.328
0.469
30.06
2
2
90
91
1.10
71
78
9.86
0.314
0.426
26.29
3
3
75
85
11.76
38
49
28.95
0.171
0.217
21.20
In at least one embodiment the method uses a cumulative FFT analysis of at least one of the corrected profiles processed following steps 1-3 described above. By summing the frequency spectra from each row the cumulative effect of the periodic features emerge as unique peaks in the spectrum. Peak amplitude is an indication of the sample periodicity while dispersion of the peak or baseline indicates the randomness in the structures. FIG. 5 compares cumulative FFT analysis results for the three tissue samples with varying degrees of softness previously referred to in Table 1. Sample 1 is ranked as having the best surface softness, and shows a unique peak at 0.26 mm that resides on a broad baseline. Comparatively sample 2 , which is ranked as having poorer softness, shows multiple peaks at larger feature sizes. The peak amplitudes and baseline level for the two samples are comparable, but the additional peaks that appear in sample 2 contribute to a reduction in softness. The lowest ranked sample 3 shows a strong peak at 0.435 mm indicating a highly periodic structure in the sheet. The combination of high periodicity and large structure size results in sample 3 having the poorest surface softness.
Another important feature from the cumulative FFT analysis is the peak dispersion. Higher dispersion in the peak indicates the distribution of structures identified is spread over a larger range. For sample 2 , the peak at 0.474 mm is broad indicating the distribution of structure sizes span a large range of values. To reduce the cumulative FFT spectrum to a useful metric that influences surface softness, the integrated peak dispersion PD given by
PD=P A ∫ x o x t A ( x ) dx
where P A is the peak amplitude and A(x) is the amplitude as a function of the feature size can be used. For example, the PD value for the first and third peaks of sample 2 is 0.16 and 0.41 respectively indicating the third peak has a stronger negative influence on surface softness because the value is larger. The calculated PD values from the cumulative FFT spectrum of a sample can be combined with other processing methods described here to develop softness correlations.
In at least one embodiment the method involves combining the different analysis methods with an automated off-line instrument to analyze crepe structures at multiple CD locations. The apparatus shown in FIG. 6 comprises an illuminating source ( 100 ) and sensor ( 105 ). The sheet sample is moved across the imaging plane by spools ( 120 ) and ( 121 ). A sample strip of varying length up to and including the full CD is placed on a spool ( 120 ). Because of geometric constraints a lead affixed to both ends of the sample and to the reels ( 120 and/or 121 ) can be used to allow image capturing at the edges. Image collection is made either asynchronous or synchronized to the reel position. In the synchronous mode, images are captured at known CD positions as the sample is translated across the imaging plane. Processing is performed to construct a CD profile for different metrics, e.g., CBI, CSI, marginal slope, % fine, etc., using the various analysis methods described here. For example, a CD analysis of CBI values coupled with moisture profile data is a useful check of how CBI variations correlate with moisture.
In at least one embodiment more than one mode of analysis is performed. For example a dual monitoring system for near simultaneous imaging of both sides of the sheet at the same location is used to monitor sheet two-sidedness. The apparatus shown in FIG. 7 consists of a multiple sensors ( 101 ) and illumination sources ( 100 ). The paper sheet ( 102 ) can be stationary or moving either continuously or at discrete increments. To prevent interference of emission beams a sheet shutter ( 110 ) is used to isolate each side from the light source to provide a dark background for improved contrast. In this mode of operation, the shutter ( 110 ) is closed on one side while the shutter on the opposite side is opened to collect the image. The procedure is then reversed to collect an image on the opposite side. Imaging made at the same location for both sides of the sheet is useful for two sidedness analysis, i.e., the difference in crepe structures between the air side and Yankee side. Higher adhesion will result in more surface structures on the Yankee side producing a softer surface.
In at least one embodiment there is an apparatus that combines multiple emission sources symmetric about the sensor normal positioned at various angles, as shown in FIG. 8 . The illuminating source can be fixed or translated to different angles. In FIG. 8 a set of emission sources ( 100 ) and ( 103 ) are positioned at angles θ 1 and θ 2 respectively. Image acquisition is made with sample emission using only one set of sources at a time. Up to n illuminating sources can be used to generate n images acquired for each set of sources. At oblique angles, e.g., θ 1 , the contrast between the high amplitude structures and low areas is enhanced resulting in clearly defined modulations indicated by the dark and light intensity regions in the image. Increasing the source angle θ will allow the light to penetrate areas between the high amplitude structures, thus decreasing the contrast between high and low structures. The change in light intensity measured as a function of the illuminating source angle can then be related to the surface structure height.
This relationship can be determined by either calibrating the system or from light scatter theory. Another application using multiple illuminating light sources is to remove embedded structures in the sheet. In this case, the images are collected with set of illuminating sources near normal to the sample and the other set at an oblique angle. The image captured with the near normal illuminating source is analyzed by FFT to remove embedded structures in the sheet that occurs from the fabric during the forming process. Embedded structures from the fabric are periodic and can be analyzed using the any of the processing methods described here for crepe structure analysis. Analysis results of the embedded structure sample can be compared with analysis results from the creped sheet image captured using the oblique illuminating source. Differences between the embedded and creped sheet analysis results are useful information for tissue makers to benchmark their process. This helps them understand if they are limited by the fabric or not to increase the crepe count in the sheet for improved softness.
In at least one embodiment there is a system configured for capturing images on-line with one or a combination of the processing methods described here. In this mode of operation real-time or near real-time analysis of the crepe structure is collected to assess product quality. Adapting any of the system configurations described here for on-line monitoring is complicated by processing speed (3000-7000 fpm) and sheet flutter (vertical movement of the sheet). Though technically challenging both of these issues can be addressed with high speed cameras and illumination sources as well as sheet stabilizing techniques. Additional complications arise for CD scanning in the translation hardware and data collection.
EXAMPLES
The foregoing may be better understood by reference to the following example, which is presented for purposes of illustration and is not intended to limit the scope of the invention.
The standardized processing methodology and apparatus of this invention were used to characterize the four tissue images shown in FIG. 9 . These images were acquired at 20× magnification. To highlight the improvement provided by this invention compared to past practices, the images were also provided to ten experienced tissue technologists skilled in the art of manual crepe counting. A calibrated length scale was provided with the images to aid in the manual analysis. The results of the manual analysis are provided in Table 2, and compared to the results from the standardized processing using the current invention in Table 3.
TABLE 2
Manual crepe analysis results from ten trained technologists
of the tissue images provided in FIG. 9. All values
provided in units of crepes/inch.
Standard
Sample
Individual Measurements
Average
Deviation
A
100, 130, 120, 100, 80, 70,
98.0
18.7
100, 90, 110, 80
B
80, 100, 100, 80, 80, 70,
84.0
10.7
90, 80, 90, 70
C
70, 90, 90, 70, 70, 50, 70,
72.0
12.3
70, 80, 60
D
60, 80, 90, 70, 70, 60, 60,
73.0
11.6
80, 90, 70
TABLE 3
Crepe analysis by the method and apparatus of this
invention for the tissue images provided in FIG. 9.
Crepe Statistics
Sample A
Sample B
Sample C
Sample D
Avg. Crepe Count
102.2
80.6
85.5
75.9
(crepes/cm)
Mean (mm)
0.249
0.315
0.297
0.334
Std. Deviation
0.113
0.138
0.136
0.170
(mm)
Median (mm)
0.234
0.297
0.285
0.304
Mode (mm)
0.195
0.197
0.204
0.216
Skewness
1.145
0.695
0.668
1.096
Kurtosis
5.877
3.458
3.667
4.872
% Fine
56.26
36.36
41.52
36.85
% Medium
35.89
49.16
47.30
44.93
% Coarse
2.47
9.02
6.42
11.39
% Very Coarse
5.38
5.46
4.76
6.83
The average crepe counts per inch (CBI) show relatively good agreement between the manual analysis and the automated analysis of this invention. However as shown by the large spread in individual measurements, there was a large amount of subjectivity in the manual analysis between technicians. Since this data was averaged from ten individuals, the average is more representative of the actual crepe frequency in the images. In practice, only one technician will be present to analyze a sample and the problem of subjectivity in manual analysis becomes clear.
On the other hand, the average crepe count in Table 3 is the average of 768 individual line scans and is a much more representative and objective value. In addition the method and apparatus of this invention provides a much greater level of detail regarding the crepe structures in the tissue sheet than is possible from the manual analysis of past practice. New information includes the mean width of the crepe structures and descriptive statistics of the frequency distribution of the crepe width sizes. Finally the distribution plot is categorized in terms of fine, medium, coarse and very coarse crepe structures.
Applying cumulative FFT and marginal CSI analysis to the set of images in FIG. 9 provides additional information on the surface structure periodicity, surface variations such as free fiber ends, fractured crepe structures, and MD crepe length, and structure density. Using this information in combination with standard crepe frequency, i.e., CBI, helps in developing tactile surface feel correlations, empirical categorization, and benchmark analysis.
The cumulative FFT analysis result shown in FIG. 10 gives insight into the surface structure periodicity. For example, a cumulative FFT analysis of a sample with high periodicity results in a spectrum with distinct peaks at the dominate feature size. This characteristic is seen in the cumulative FFT spectrum for sample B in FIG. 10 , which shows three distinct peaks at 3.4, 2.0, and 1.4 mm −1 that reside on top of a broad baseline structure. In contrast, sample A shows a lower periodicity with only a few low amplitude peaks at 0.31, 3.24, 3.71, and 4.63 mm −1 on the broad baseline structure. If little or no periodicity is maintained in the CD as the analysis marches along the MD, then no distinct peak will appear. In this case, the cumulative FFT spectrum would appear only as a broad baseline structure because periodic CD features will not constructively build to form a peak. Samples with high periodicity have crepe structures that are well defined in the MD with length scales greater than low periodicity samples. The combination of periodic structures with long MD length scales contributes to the high amplitude well defined peaks in the cumulative FFT spectrum, as shown in FIG. 10 for sample B. Surfaces with these characteristic features will have a coarser tactile feel because the density of structures in contact with one's finger is less compared to a sample with randomly distributed structures.
Application of the marginal slope analysis for the sample set of images ( FIG. 9 ) is shown in FIG. 11 . In this case, DC/DF represents the change in crepe frequency over the change in filter points used in the Savitsky-Golay filtering performed on each row of pixels. As the number of points used in the filter increases, the change in crepe frequency asymptotically approaches a consistent value, i.e., as the filter points go to infinity DC/DF goes to zero because the variations in the line profile are completely smoothed out. Therefore, marginal slope analysis will show the greatest change starting at lower filter points. For imaged samples with high periodicity, e.g., sample B, and/or large crepe structures, the marginal slope shows the least sensitivity because the overall underlying pattern is retained. In contrast, samples with higher randomness and crepe frequency, e.g., sample A, will have higher sensitivity to the change in the number of points used for filtering. A summary of the marginal slope results is presented in Table IV for the initial slope, e.g., points 2 - 10 in FIG. 11 .
TABLE 4
Summary of marginal slope analysis results
for the sample set of images in FIG. 9.
Predicted
Marginal
Periodicity
Surface feel
Sample
CBI
Slope
Ranking
(1 = best, 4 = worst)
A
102
1.008
4
1
B
81
0.114
1
4
C
85
0.967
3
2
D
76
0.533
2
3
From Table 4, sample C shows nearly the same marginal slope as sample A, yet the CBI results are significantly different. In this case, the contributing factor is from fractured crepe structures and free fiber ends that increase the marginal slope sensitivity. In addition, the cumulative FFT result for sample C shows some periodicity with distinct peaks at 1.85, 2.32, and 3.24 mm −1 , but at low amplitude. Contribution from these surface structures affects the periodicity resulting in higher dispersion around the three peaks.
Of the four samples from FIG. 9 , sample D has the lowest CBI value and second lowest marginal slope. From the cumulative FFT analysis, sample D has a distinct peak at 2.16 mm −1 that has higher amplitude and is narrower compared to the peaks from sample C. The lower marginal slope value results from the larger crepe structures and decreases the sensitivity for the number of filter points used. This sample also has more randomness in the crepe frequency compared to sample B resulting in a lower amplitude.
Based on the cumulative FFT, marginal slope analysis, and CBI for the set of images, periodicity and predicted surface softness ranking is listed in Table 4. As discussed, above sample A has clear differences in CBI, marginal slope, and cumulative FFT spectrum compared to the other samples. Whereas differences between samples B, C, and D are vague if only CBI is used as a comparative metric, thus requiring a more detailed analysis using cumulative FFT and marginal slope analysis.
While this invention may be embodied in many different forms, there are shown in the drawings and described in detail herein specific preferred embodiments of the invention. The present disclosure is an exemplification of the principles of the invention and is not intended to limit the invention to the particular embodiments illustrated. All patents, patent applications, scientific papers, and any other referenced materials mentioned herein are incorporated by reference in their entirety. Furthermore, the invention encompasses any possible combination of some or all of the various embodiments described herein and incorporated herein. Finally the invention encompasses any and all compositions disclosed or incorporated herein, any and all apparatuses disclosed or incorporated herein, and/or any and all methods of using those compositions and/or apparatuses disclosed or incorporated herein.
The above disclosure is intended to be illustrative and not exhaustive. This description will suggest many variations and alternatives to one of ordinary skill in this art. All these alternatives and variations are intended to be included within the scope of the claims where the term “comprising” means “including, but not limited to”. Those familiar with the art may recognize other equivalents to the specific embodiments described herein which equivalents are also intended to be encompassed by the claims.
All ranges and parameters disclosed herein are understood to encompass any and all subranges subsumed therein, and every number between the endpoints. For example, a stated range of “1 to 10” should be considered to include any and all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10; that is, all subranges beginning with a minimum value of 1 or more, (e.g. 1 to 6.1), and ending with a maximum value of 10 or less, (e.g. 2.3 to 9.4, 3 to 8, 4 to 7), and finally to each number 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 contained within the range.
This completes the description of the preferred and alternate embodiments of the invention. Those skilled in the art may recognize other equivalents to the specific embodiment described herein which equivalents are intended to be encompassed by the claims attached hereto. | The invention embodies methods and apparatuses to monitor and control the characteristics of a creping process. The method involves measuring optical properties of various points along a creped paper sheet and converting those measurements into characteristic defining data. The invention allows for determining the magnitude and distribution of crepe structures and their frequency and distribution. This allows for the generation of information that is accurate and is much more reliable than the coarse guessing that is currently used in the industry. Feeding this information to papermaking process equipment can result in increases in both quality and efficiency in papermaking. | 6 |
The present application is a 35 USC 371 national phase application from and claims priority to international application PCT/IL02/00503, filed 24 Jun. 2002, established under PCT Article 21(2) in English, which claims priority to Israeli patent application Ser. No. 143993, filed 26 Jun. 2001, which applications are incorporated by reference herein.
FIELD OF THE INVENTION
The present invention relates to a method for incinerating combustible materials, particularly waste materials, including hazardous and bio-hazardous waste materials.
BACKGROUND OF THE INVENTION
The disposal of waste is a serious problem to governments, especially municipal governments. The waste disposal process is regulated by increasingly stricter standards since some wastes are toxic. In the case of industrial waste, there are even more problematic materials, such as petrochemicals, PCBs (polychlorinated biphenyls), etc. than in common, non-industrial waste. Additionally, medical and other biological waste is often hazardous and requires complete sterilization and decomposition.
Previously, other methods of waste disposal were more attractive than incineration. Landfills, for example, were used instead of incineration since the cost of disposing waste at a landfill was far less than that of incineration. However, increasingly more severe environmental standards have made landfills less attractive, primarily because of the increased awareness that toxic chemicals, over long periods of time, percolate through the ground contaminating aquifers. Similarly, the ever increasing quantity of waste make landfills and other methods physically impractical.
Accordingly, destructive, degradative processes such as incineration have become more popular. Destructive techniques like incineration must efficiently turn waste into innocuous end-products. This is a particularly acute problem in incineration where burning hazardous waste requires high temperatures so that the resulting decomposition products are environmentally benign. The high temperatures needed and the large quantities of waste involved require the development of incinerators that are economically and environmentally efficient. The emissions from such products are generally gaseous and must comply with standards set by international and governmental agencies. Similarly, solid and particulate wastes of incineration, such as slag, bottom ash and fly ash, must be neutered to remove harmful effects to the environment.
Examples of recently proposed incineration methods and incinerators can be found in U.S. Pat. Nos. 5,752,452 and 5,179,903, and WO 96/24804, Abboud. U.S. Pat. No. 5,179,903 and WO 96/24804 describe recycled flue gases which are augmented with oxygen, U.S. Pat. No. 5,752,452 describes a system with lances which inject oxygen into a heating zone at a velocity of at least 350 ft/sec.
However, despite improvements in incinerators and incineration processes, capital and maintenance costs are still very high. In addition, effluents emitted into the environment still require further reduction.
SUMMARY OF THE PRESENT INVENTION
An object of the present invention is to provide a process which maximizes the rate of incineration and throughput in waste incinerators while minimizing gas emissions and solid waste produced.
It is a further object of the present invention to provide an economical incineration process for use with industrial, consumer and biological wastes, including hazardous waste.
It is yet another object of the present invention to minimize the size of the required incinerator and flue gas purification system, thereby minimizing the required investment and maintenance costs.
A further object of the present invention is to provide an economical, environmentally friendly process which can be applied to large industrial installations, such as electricity generating plants, which burn large quantities of fossil fuels.
There is thus provided in accordance with the present invention a process for incinerating combustible material including the step of delivering combustible material and inlet gases to a primary combustion chamber, the inlet gases having an oxygen content of at least 50 vol. %. This is followed by burning the combustible material with the oxygen of the inlet gases in a primary combustion chamber producing flue gases and solid particulates as thermal decomposition products of the burnt combustible material. The flue gases and particulates are then passed to a secondary combustion chamber where further combustion occurs. The flue gases exiting from the secondary combustion chamber are cooled. A portion of the cooled flue gases is returned to at least one of the combustion chambers where the cooled gases moderate the temperature in the at least one chamber. Finally, the remaining portion of the cooled flue gases is passed on to a flue gas purification system where pollutants in the flue gases and particulates are substantially converted to benign compounds or removed entirely before the flue gases are emitted into the atmosphere.
Additionally, there is provided in accordance with the present invention a process which further includes the step of monitoring the value of at least one parameter in at least one combustion chamber, the parameter being a function of the thermal decomposition of the combustible material in at least one combustion chamber. This is followed by comparing the value of the at least one monitored parameter with at least one predetermined value for that parameter, the comparison being effected by a control device. Finally, the result of the comparison is communicated to a means for controlling the portions of cooled flue gases returned to the at least one combustion chamber and the flue gas purification system. The means for controlling the portions adjusts the relative sizes of the two portions accordingly.
Additionally, in accordance with a preferred embodiment of the present invention the at least one parameter in the monitoring step is temperature. The temperature can be monitored in the primary combustion chamber or in the secondary combustion chamber or in both chambers.
Further, in accordance with a preferred embodiment of the present invention, the at least one parameter in the monitoring step is the concentration of carbon monoxide or the concentration of oxygen or the concentration of both simultaneously. These concentrations can be measured in the effluent of the secondary combustion chamber.
In accordance with a preferred embodiment of the present invention, the means for controlling the amount of cooled gases are valves.
Additionally, in accordance with a preferred embodiment of the present invention, the inlet gases of the delivering step are delivered in two high concentration oxygen streams, one inlet gas stream positioned adjacent to the burning waste and the other above the flames of the burning waste, the amount of oxygen from each stream controlled so that the temperature of the burning waste is maintained at a temperature that does minimal damage to the floor of the primary combustion chamber, while ensuring complete combustion of the waste and an oxygen volume % in the system's effluent within regulatory limits.
Further, in accordance with a preferred embodiment of the present invention the oxygen content of the inlet gases is at least 80 vol. %.
Additionally, in a preferred embodiment of the present invention, the oxygen content of the inlet gases is at least 90 vol. %.
Further, in a preferred embodiment of the present invention, the oxygen content of the inlet gases is between about 90 vol. % and 95 vol. %.
Additionally, in accordance with a preferred embodiment of the present invention, the burning step in the primary combustion chamber is effected at a temperature from about 1100° C. to about 2000° C.
In another preferred embodiment of the present invention, the burning step in the primary combustion chamber is effected at a temperature from about 1200° C. to about 1750° C.
Additionally, in a preferred embodiment of the present invention, the burning step in the primary combustion chamber is effected at a temperature from about 1300° C. to about 1500° C.
Further, in yet another embodiment of the present invention, combustion in the secondary combustion chamber of the first passing step is effected at a temperature from about 850° C. to about 1500° C.
In another embodiment of the present invention, combustion in the secondary combustion chamber of the first passing step is effected at a temperature from about 950° C. to about 1350° C.
Additionally, in yet another embodiment of the present invention, combustion in the secondary combustion chamber of the first passing step is effected at a temperature from about 1050° C. to about 1200° C.
In another embodiment of the present invention, the process further includes the step of adding at least one reduced nitrogen compound into the second combustion chamber to destroy nitrogen oxide gases. Typically, the at least one reduced nitrogen compound can be ammonia or urea.
Further, in a preferred embodiment of the present invention, the process further includes the step of separating solid particulates from the flue gases after the gases are cooled.
Additionally, in a preferred embodiment of the invention, the at least one combustion chamber of the returning step is the primary combustion chamber.
Finally, in a preferred embodiment of the present invention, the cooled flue gases are returned to the primary combustion chamber proximate to the flame produced by burning combustible material in that chamber. In another embodiment, the cooled flue gases are returned to the primary combustion chamber proximate to the bottom ash and slag.
In yet another preferred embodiment of the present invention, the at least one combustion chamber of the returning step is the secondary combustion chamber.
Finally, the present invention can be used with combustible material which is waste, including hazardous waste, or fuels.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will be understood and appreciated more fully from the following detailed description taken in conjunction with the drawings in which:
FIG. 1 is a flow diagram illustrating a preferred embodiment of the process of the present invention;
FIG. 2A is a schematic view of an incinerator operative in accordance with the present invention;
FIG. 2B is a schematic view of a typical purification system which can be used with an incinerator operative in accordance with the present invention; and
FIG. 3 is a schematic diagram illustrating another preferred embodiment of the process of the present invention.
Similar elements in the Figures are numbered with similar reference numerals.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Reference is now made to FIG. 1 , which shows a flow diagram of a preferred embodiment of an incineration process generally referenced 110 , in accordance with the present invention. Process 110 is particularly preferred when used to incinerate industrial, commercial and/or biological waste. The description herein below, as well as the accompanying Figures, describe the process in terms of such waste. However, while the above process 110 has been discussed as a process for the incineration of waste, the system can also be used to burn any fuel, producing energy in a clean, cost efficient manner. In lieu of municipal or industrial waste, process 110 can be used to burn fuels such as natural gas, fuel oil, and coal. These fuels, however, are to be viewed as non-limiting examples.
Process 110 includes a primary combustion chamber (PCC) 12 into which waste is fed 51 via a conduit (not shown). Inlet gases containing at least 50 vol. %, preferably at least 80 vol. %, and most preferably at least 90 vol. % oxygen, usually between about 90 vol. % to 95 vol. % oxygen, are also passed 53 , via a conduit (not shown), into PCC 12 , typically in the region immediately proximate to the burning waste. The waste is burned in an excess of the stoichiometric amount of oxygen. The waste is burned in PCC 12 at temperatures maintained between about 1100 to 2000° C., preferably between about 1200 to 1750° C., and even more preferably between about 1300 to 1500° C. Because of the high oxygen concentrations used in primary combustion chamber 12 , a significant percentage of the material burned undergoes complete oxidation. Oxygen lancing and other methods to introduce supplementary oxygen are therefore not required.
Flue gases mixed with small solid particulates resulting from incineration rise from PCC 12 and pass 55 , via a conduit (not shown), into a secondary combustion chamber (SCC) 14 . Partially combusted flue gases are further combusted in SCC 14 to more completely oxidized gases using the residual oxygen arriving from PCC 12 . In SCC 14 , the temperature is maintained within the range of from about 850 to 1500° C., preferably from about 950 to 1350° C., and even more preferably from about 1000 to 1200° C.
Optionally, materials which destroy nitrogen oxide gases (NOx) are fed 57 , via a conduit (not shown), into SCC 14 . Typically, these materials are reduced nitrogen compounds such as ammonia or urea which convert the NOx gases formed in PCC 12 and SCC 14 into nitrogen and water. Since the amount of nitrogen comprising the inlet gases passed 53 , via a conduit (not shown), into PCC 12 is small, the amount of NOx present in the system is not great. In some embodiments, the materials which destroy nitrogen oxide gases may be employed without a catalyst; in other embodiments, a catalyst may be required. Preferably, PCC 12 and SCC 14 are contained in a single structure, but each can be located in separate structures, when necessary.
The flue gases are conveyed 59 via a conduit (not shown) to a heat exchanger 22 . Typically, heat exchanger 22 may be a boiler which removes heat from the flue gases. The energy removed, usually as steam, is conveyed 61 , via a conduit (not shown), to an energy converter 18 , often a turbogenerator. Alternatively, any heat recovery system from which electricity or steam can be withdrawn 63 can be employed. Any electricity generated or steam removed can be returned to the incineration plant or distributed to outside consumers.
After emerging from heat exchanger 22 , the flue gases have a temperature of about 230 to 270° C., preferably about 250° C. The gases are transferred 65 via a conduit (not shown) to a particulate separator 26 , typically a cyclone separator, which via a conduit (not shown), removes 69 fly ash 27 from the flue gases. The removed fly ash 27 is collected, “bagged” and sent to a toxic waste disposal site. The use of a particulate separator 26 at this stage of process 110 is optional. Alternatively, particulates can be removed exclusively in flue gas purification system 29 discussed below. As another alternative, purification system 29 can include a particulate remover which supplements particulate separator 26 .
Two valves (not shown) located between particulate separator 26 and flue gas purification system 29 divide the flue gases into two portions. The percentage of flue gas that is recycled 73 through a conduit (not shown) and the percentage of flue gas passed 71 via a conduit (not shown) directly on to a flue gas purification system 29 for further purification is determined by some parameter(s) of PCC 12 and/or SCC 14 . Typically, the parameter is its (their) temperature(s) or the concentration of carbon monoxide and/or oxygen on the downstream side of SCC 14 .
The flue gases that are passed on 71 via a conduit (not shown) for further purification reach flue gas purification system 29 , details of which are not shown. The exact nature of purification system 29 depends on the waste being incinerated, the gases and particulates emitted, and the environmental standards which must be met. Typically, flue gas purification system 29 contains a particulate remover, which supplements optional particulate separator 26 , discussed above, and sometimes serves as the sole particulate remover in process 110 . Generally, the particulate remover in purification system 29 traps finer particles than optional particulate separator 26 . Typically, purification system 29 also contains a scrubber to neutralize acid gases. Other apparatuses commonly used for purifying effluent gases can be added as needed to attain the required effluent emission standards before the gases are expelled 81 to the atmosphere.
Another portion of the flue gases is recycled 73 via a conduit (not shown) to PCC 12 . Typically, the recycled, cooled flue gases are returned 73 A via a conduit (not shown) to PCC 12 directly above the flame, thereby removing heat from PCC 12 and transferring it to heat exchanger 22 via SCC 14 . In another embodiment, the recycled flue gases can be returned 73 B via a conduit (not shown) directly to SCC 14 . In yet another embodiment, the flue gases can also be recycled 73 C via a conduit (not shown) through bottom ash and slag 17 lying at the floor of PCC 12 . Finally, in other embodiments, the cooled flue gases can be returned to both PCC 12 and SCC 14 . Because PCC 12 operates at temperatures in excess of 1300° C., the bottom ash becomes vitrified 75 when cooled. Some ash is carried 79 by convection to SCC 14 . Cooled slag and vitrified bottom ash 17 are periodically removed 77 to a slag and bottom ash receptacle (not shown) for disposal.
Reference is now made to FIG. 2A which shows a schematic view of an incinerator system 210 operated in accordance with the process 110 of the present invention shown in FIG. 1 . The system 210 permits a better understanding of process 110 presented in FIG. 1 . The system shown in FIG. 2A , however, is presented by way of example only and should not be considered as limiting.
System 210 includes a primary combustion chamber 12 into which waste 19 is fed from a waste feed 10 . There is an inlet gas feed array 15 which delivers inlet gases for combustion, the gases typically being composed of at least 90 vol. % oxygen. Waste 19 is burned in primary combustion chamber (PCC) 12 . The inlet gases are brought from array 15 proximate to the burning waste in PCC 12 . The high concentration of oxygen in the inlet gases fed to primary combustion chamber 12 accelerates the rate of combustion of waste 19 . The temperature in PCC 12 is also significantly higher than temperatures generated when air alone is used. The higher temperatures attained easily crack and shatter solids, facilitating their incineration. Materials that do not burn in air, or do so only incompletely, burn easily in inlet gases with a high oxygen content, often to near completion. Since the oxygen concentration used in the process of the present invention is so high, burning is much more complete and there is no need for selectively introducing lanced oxygen. Because the rate of combustion is faster than in currently used incinerators, primary combustion chamber 12 can be made smaller while throughput will be greater than in prior art incinerators.
PCC 12 has a bottom grating comprised of slats, which are preferably adapted to be rotatable or otherwise movable so as to rotate or otherwise agitate the burning waste. The grating can be made from, or covered with, ceramic materials which protect it from the elevated temperature of combustion. Typically, every other grating slat is moved periodically, turning over the burning waste, permitting more thorough and rapid combustion. The lower parts of the walls of PCC 12 must also be protected from the heat, usually using ceramic tiling as shields. Alternatively, the walls and the grating can be cooled with water flowing through adjacent water pipes. It is readily apparent to one skilled in the art that instead of grating slats at the bottom of primary combustion chamber 12 , the floor of chamber 12 can include rotating metal cylindrical rollers or any other means that can periodically move and/or rotate the burning waste.
Slag and bottom ash 17 from PCC 12 are cooled and emptied into an ash and slag receptacle (not shown) via a slag channel 16 . Because of the high temperatures (>1300° C.) in the primary combustion chamber 12 , the bottom ash 17 is vitrified when cooled and encapsulated in a glass-like crust. The encapsulation insulates and neutralizes harmful materials making them usable for civil engineering projects such as road beds without the need for further processing.
Gases and fly ash emitted from the burning waste as well as residual oxygen from PCC 12 enter a secondary combustion chamber 14 where additional combustion occurs. An array 30 of nozzles in the wall of primary combustion chamber 12 injects cooled, recycled flue gases into PCC 12 ; typically these recycled gases enter PCC 12 immediately above flames 11 . The cooled, recycled flue gases entering from array 30 have a typical temperature of approximately 250° C. and they maintain the temperature in primary combustion chamber 12 at a predetermined temperature, generally about 1300 to 1500° C. Similarly, they cool the gases rising from PCC 12 into SCC 14 to temperatures between about 1000 to 1300° C.
Optionally, ammonia or urea are added to the flue gas in SCC 14 reducing the nitrogen oxide gases produced in PCC 12 and SCC 14 to nitrogen and water. PCC 12 and SCC 14 can be constructed as any one of several types of chambers, such as rotary kiln, fixed hearth or other types of ovens.
The gases continue on from secondary combustion chamber 14 to an heat exchanger 22 , typically a boiler. Heat exchanger 22 removes heat from the flue gases, generally forming steam which is led to a turbogenerator (not shown). The turbogenerator can be connected to an electric grid from which electricity can be delivered directly to consumers or returned to the incineration plant for use within the plant. Alternatively, the steam itself, or a mixture of steam and electricity generated by the heat exchanger/boiler 22 and turbogenerator (not shown) respectively, can be sold. By the time the gases and fly ash emissions from the burnt waste reach an optional blower 24 , the temperature of the gases has been reduced to approximately 250° C.
The fly ash that passes through optional blower 24 enters an optional cyclone separator 26 which precipitates the bulk of the fly ash passing through blower 24 . The cyclone separator 26 may be any cyclone separator commercially available used to separate particulates from gases. A single cyclone or multiple cyclones can be used.
It should be noted that there is a significant reduction in the amount of fly ash produced by the process of the present invention. The reduction in fly ash is a direct consequence of the very high percentage of oxygen introduced with the inlet gases. The high percentage of oxygen reduces the total amount of inlet gases provided to primary combustion chamber 12 , which in turn leads to a smaller volume of carrier gas for ash generated by incineration. More of the ash produced remains as bottom ash. Since fly ash traps poisonous materials found in flue gases, such as dioxins and heavy metals, the law requires that fly ash be gathered and delivered to a toxic disposal dump. Any reduction in fly ash therefore results in a reduction in waste treatment expense.
The bulk of the emitted waste gases, the flue gas, is returned via a recycling line 28 to primary combustion chamber 12 . The recycled flue gas is at a temperature of approximately 250° C. and enters PCC 12 through array 30 in the wall of primary combustion chamber 12 . Generally, the gases enter the chamber proximate to and above flames 11 . The cooled recycled flue gas functions as a coolant keeping the temperature in primary combustion chamber 12 at the predetermined temperature, typically 1300-1500° C. Typically, the recycled flue gases reenter the system directly into PCC 12 above flames 11 therein; optionally they can also be recycled directly to SCC 14 or into the bottom ash and slag 17 on the floor of PCC 12 . Typically, an array of conduits is used for reintroducing the recycled flue gas, but in other embodiments, a single point of entry for the recycled flue gases may be employed.
Part of the flue gases from blower 24 enters a cleaning line 32 . Valves 31 A and 31 B determine how much, and when, flue gases enter cleaning line 32 and recycling line 28 . Using 90 vol. % oxygen and a typical mix of Israeli municipal waste, the mixture of flue gases generated and entering these lines has a typical approximate composition of oxygen 6 vol. %, nitrogen 5 vol. %, CO 2 43 vol. % and steam 46 vol. %. If the inlet gases fed to primary combustion chamber 12 had been air (approximately 21 vol. % oxygen) and not a gas mixture containing at least 90 vol. % oxygen, the nitrogen content of the flue gases entering cleaning line 32 and recycling line 28 would have risen to approximately 66 vol. %.
Valves 31 A and 31 B are connected to a control system which monitors a parameter, typically the temperature, of the gases exiting primary combustion chamber 12 and/or secondary combustion chamber 14 . If the temperature is higher than required, a larger percentage of the flue gases is recirculated to the primary combustion chamber; if the temperature in the primary combustion chamber is lower than required, the amount of flue gases that is returned is decreased. If, for example, the temperature in PCC 12 is 1750° C. and the temperature in SCC 14 is 1100° C., the approximate percentage of flue gases recycled is 60 vol. % while 40 vol. % are passed via line 32 directly to the flue gas purification system 310 shown in FIG. 2 B and discussed below.
Typically, a device, for example a thermocouple, is used to measure the temperature inside PCC 12 and/or SCC 14 , while a temperature controller compares the measured PCC 12 and SCC 14 temperatures, with one or more temperature set points. The controller then opens or closes the two valves accordingly, returning the required amount of recycled flue gases to PCC 12 and/or SCC 14 . The recycling of cooled flue gases ensures better control of temperature in primary combustion chamber 12 than when recycling is absent. It also increases the degree of combustion of the flue gases.
Reference is now made to FIG. 2B , where a schematic view of an exemplary purification and scrubbing system 310 of the incinerator plant is shown. The configuration of devices in FIG. 2B are shown merely by way of example and the scope of the present invention is not intended to be limited thereby.
Cleaning line 32 continues into the purification system 310 of the plant where the amount of effluent solid and flue gases is reduced. These gases and solids are led into an electrostatic precipitator (ESP) 34 which complements or functions in place of cyclone separator 26 discussed above. In ESP 34 much of the remaining fly ash is removed. In ESP 34 , fly ash particulates are charged by a high voltage source and drawn to a conductive plate of opposite charge where the particulate's charge is dissipated. The ash is then precipitated and collected.
The flue gases are then sent via a line 42 to a scrubber heat exchanger 36 which removes heat from the system. The gases enter the lower part of a scrubber 40 where the temperature is less than 100° C. and much of the water vapor in the flue gases condenses. In scrubber 40 , drops of a basic solution containing calcium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate or some other such alkaline compound are injected. These neutralize acid gases such as sulfur dioxide and any residual nitrogen oxides not destroyed by ammonia or urea optionally added in secondary combustion chamber 14 . The scrubbed gases then reenter heat exchanger 36 , via a line 38 , where they are reheated using the heat previously withdrawn from the flue gases before these gases entered the lower part of scrubber 40 . The reheated gases then enter a line 46 , where an activated carbon injector 44 injects carbon into line 46 , so that contaminants, among them dioxins and furans, are adsorbed. The carbon also traps other contaminants including heavy metal and heavy metal oxide particulates.
The injected activated carbon and gas effluents advance through line 46 and are deposited onto a fabric filter 50 , which removes the injected active carbon from the flue gases. Residual gases such as oxygen and nitrogen are then led through a line 48 to a stack 52 where they are emitted into the air, usually with the assistance of a blower 49 located at the bottom of the stack.
When the inlet gases contain at least 90% oxygen, the amount of effluent gases emitted from stack 52 is about 5 times less than the amount emitted by currently used incinerators. Typically, approximate percentages of the emitted gases using the process of the present invention are 6 vol. % oxygen, 5 vol. % nitrogen, 20 vol. % water vapor and 70 vol. % carbon dioxide.
The reduction in nitrogen and the large amount of completely oxidized carbon in the form of carbon dioxide are a direct result of the use of inlet gases with a very high oxygen content followed by recycling of flue gases into the primary combustion chamber. The reduction in water vapor is a consequence of the condensation of a large percentage of the vapor in scrubber 40 discussed above.
It should be apparent to one skilled in the art that the exact configuration of devices used to clean the effluent after it enters cleaning line 32 is to a degree variable and/or optional. Other types of scrubbers and filters known in the art can be used. Similarly, some of the devices discussed above may be absent entirely while others not shown can be added. Cleaning devices at different plants would be expected to vary depending on the nature of the waste being burned and the environmental standards which must be met.
The inlet gases used to burn waste in primary combustion chamber 12 of the process discussed herein above should typically contain at least 80 vol. %, preferably at least 90 vol. %, but generally between 90 vol. % and 95 vol. %, oxygen. This level of oxygen content (90-95 vol. %) is readily attained by using a vapor pressure swing adsorption (VPSA) device, such as the one produced by Praxair Inc. A VPSA device absorbs nitrogen from air and passes the rest of the gases, mainly oxygen, to primary combustion chamber 12 at relatively low cost. VPSA separates nitrogen from air by molecular sieving. Nitrogen is adsorbed at low pressures in the sieve and then removed by vacuum. Presently, this method is the most economical way to obtain gas fractions having such high percentages of oxygen. Any attempt to use higher concentrations of oxygen to increase the performance of the incinerator would increase the cost of producing the inlet gas because it would require distillation of liquefied air.
The use of VPSA as discussed above or, alternatively, the related pressure swing adsorption (PSA) process to produce inlet gases containing a high percentage of oxygen should be viewed as non-limiting. Devices employing membrane technology also can be used to produce inlet gases with higher than atmospheric oxygen content but these typically are only 40 to 60 vol. %.
Since there is likely to be a reduction by a factor of about 5 in effluent gases at the incinerator's stack when the inlet gases of the incinerator include at least 90% oxygen (based on absolute amount of weight per ton of waste), there is a concomitant reduction in the size and cost of the apparatus required to clean up effluent gases. Similarly, costs of the incinerator are reduced because of the faster combustion and higher throughput. In addition, because of the reduction in fly ash and the vitrification of bottom ash in the system, waste disposal costs are reduced. Finally, because nitrogen forms a much smaller portion of the inlet gases, energy lost in heating nitrogen is reduced. This energy may be retrieved for profitable use elsewhere.
Reference is now made to FIG. 3 which schematically shows another embodiment of the present invention. FIG. 3 includes a primary combustion chamber (PCC) 12 , a secondary combustion chamber (SCC) 14 , and their control systems 120 , 122 and 124 . It also includes an inlet gas feed array 15 , an auxiliary inlet gas feed array 115 and a recycled gas flue array 30 , positioned in the aforementioned chambers.
In this, as in previous embodiments, a high oxygen concentration is fed into PCC 12 proximate to the burning waste at the floor of PCC 12 . Oxygen is delivered through inlet gas feed array 15 , which, because of the high concentration of oxygen delivered, generates very high temperatures near the burning waste 11 . These temperatures may adversely effect the structure of PCC 12 and can require different, more heat resistant, more costly materials from which to construct PCC 12 .
In order to reduce combustion temperatures in the bottom region of PCC 12 , the present embodiment contemplates limiting the total amount of oxygen supplied to the primary chamber by inlet gas feed array 15 . Limiting the oxygen introduced by array 15 , but not the high concentration of the oxygen, reduces the temperature at, or near, the floor of PCC 12 .
With the reduction in total amount of oxygen introduced through inlet gas feed array 15 , some waste, and the flue gases generated therefrom, may be incompletely oxidized. In order to ensure that all the waste and flue gases are substantially completely burned, there is positioned in PCC 12 a second gas feed array carrying a high concentration of oxygen to PCC 12 . This second array, herein denoted as an auxiliary inlet gas feed array 115 , supplies a high concentration of oxygen, typically in excess of 90%, over the burning coals and into the flue gases rising therefrom. The oxygen fed through auxiliary inlet gas feed array 115 produces substantially complete combustion of the flue gases generated by the burning waste in PCC 12 , while permitting operation of PCC 12 at lower temperatures. Even if oxygen provided by auxiliary inlet gas feed array 115 increases the temperature of the exiting flue gases, little increase in temperature results in the burning waste adjacent the floor of PCC 12 and little damage to the floor of PCC 12 occurs.
The temperature of the exiting flue gases is moderated by recycled gases introduced from an array of nozzles 30 through valves 130 , the nozzles generally located in the wall of SCC 14 or in the upper region of PCC 12 . The temperature of the exiting flue gases is measured by a thermocouple, pyrometer or other temperature monitoring instrument 142 B connected to a temperature control unit 120 which controls the operation of valves 130 .
Using two high concentration oxygen sources, inlet gas feed array 15 and auxiliary inlet gas feed array 115 , allows for substantially complete combustion of the waste at generally lower temperatures in, or proximate to, the burning waste located at, or near, the bottom of PCC 12 .
The amounts of oxygen brought into PCC 12 and needed to maintain relatively low combustion temperatures there can be controlled in several ways. Temperature control can be effected by monitoring the oxygen concentration in the effluent emerging from the system's stack 52 . As described above, flue gas concentrations entering the atmosphere must meet strict regulatory requirements. An oxygen monitoring instrument 132 can be inserted into, or positioned near, the outlet of stack 52 to monitor the oxygen vol. % of the effluent. Data relating to the concentrations thus measured are then fed to an oxygen concentration control unit 122 . When the oxygen concentration in the effluent emerging from stack 52 is lower than required by regulations, the amount of oxygen provided by auxiliary oxygen feed array 115 is increased; when the amount of oxygen is higher than required by regulations, the amount of oxygen supplied by auxiliary oxygen feed array 115 is reduced.
As an alternative to an oxygen monitoring instrument 132 positioned at the outlet of stack 52 , oxygen can be monitored by measuring oxygen content of the recycled gases delivered by recycled gas flue array 30 and entering either PCC 12 or SCC 14 . The percentage oxygen content at stack 52 is related to the oxygen content in the recycled gases arriving from recycled gas flue array 30 . Therefore, the composition of the recycled gases entering either PCC 12 or SCC 14 can be used to determine the over or under abundance of oxygen at stack 52 .
In yet other embodiments of the present invention, two oxygen monitoring instruments can be used to determine the oxygen content exiting stack 52 . One instrument 132 can be positioned at stack 52 while the other can be located at the point where recycled flue gases are delivered by array 30 .
An alternative method for controlling the system is by monitoring the temperature in PCC 12 . At least one thermocouple or pyrometer 142 A is placed near, or at, the flames 11 of the burning waste. The results of these temperature measurements then are fed into a control unit 124 , the burning waste temperature control unit, and compared to a predetermined temperature setting. The amount of oxygen provided to PCC 12 by both gas inlet arrays 15 and 115 then is adjusted to maintain a predetermined temperature setting at flames 11 by operating valves 126 and 128 , respectively. By controlling temperature, the effluent oxygen concentration at stack 52 is also kept within regulatory limits.
It should be readily apparent to one skilled in the art that there is a reciprocal relationship between the amount of oxygen being supplied through valves 126 and 128 of inlet gas feed array 15 and auxiliary inlet gas feed array 115 , respectively. When more oxygen is required at array 15 , generally less oxygen is required at array 115 for a given required flame temperature.
When the temperature of the burning material is too high, valve 126 , controlled by burning waste temperature control unit 124 , reduces the flow of oxygen from inlet gas feed array 15 above the burning coals. Control unit 124 is separate from another control unit, the temperature control unit 120 , which monitors temperature at the exit of the secondary combustion chamber (SCC) 14 . This temperature, as discussed above, is effected by means of two valves 31 A and 31 B ( FIG. 2A ) which determine the amount of recycled cooled flue gases returned to PCC 12 and SCC 14 or sent to stack 52 by recycling line 28 ( FIG. 2A ) or cleaning line 32 (FIG. 2 A), respectively.
It can readily be seen that the temperature of the burning coals as measured by measuring instrument 142 A and controlled by control unit 124 through valve 126 and gas feed array 15 , the oxygen monitoring instrument 132 at stack 52 and its oxygen control unit 122 through valve 128 and auxiliary gas feed array 115 , and temperature monitoring instrument 142 B through temperature control unit 120 and valve 130 of recycled flue gas array 30 form three control loops which are functionally interconnected. Generally, changes in one have a discernible effect in the other two control loops.
The embodiment shown in FIG. 3 moderates and controls temperature better than in currently available furnaces. This embodiment with its auxiliary oxygen feed array 115 and recycled flue gas array 30 , the latter positioned either in the walls of secondary combustion chamber (SCC) 14 or the upper region of PCC 12 , permits moderation of the temperature at every stage of the combustion process. Furnace temperatures, irrespective of the type of the furnace used, can be maintained so that damage to PCC 12 is minimized.
It will be appreciated by persons skilled in the art that the present invention is not limited by what has been particularly shown and described herein above. Rather the scope of the invention is defined solely by the claims that follow. | A process for incinerating combustible materials including the steps of: delivering combustible material and inlet gases to a primary combustion chamber, the inlet gases having an oxygen content of at least 50 vol %; burning the combustible material with the oxygen of the inlet gases in the primary combustion chamber producing flue gases and solid particulates as thermal decomposition products of the burnt combustible material; passing the flue gases and particulates to a secondary combustion chamber where further combustion occurs; cooling the flue gases exiting the secondary combustion chamber; returning a portion of the cooled flue gases to at least one of the combustion chambers where the cooled gases moderate the temperature in the at least one chamber; and passing the remaining portion of cooled flue gases on to a flue gas purification system where pollutants in the flue gases and particulates are substantially converted to benign compounds or removed entirely before the flue gases are emitted into the atmosphere. | 5 |
FIELD OF THE INVENTION
The present invention relates to a method and apparatus for determining the position of an unattached sensor in free space. More specifically, the invention relates to a device and method of determining the position and orientation of a line of sight device, such as a targeting device used by the pilot of an aircraft.
BACKGROUND OF THE INVENTION
Determining the position and orientation of objects in free space has many applications. Specific applications include targeting systems used in conjunction with various aircraft, computer peripherals which utilize the position sensing apparatus to position a cursor, and many other pointing applications. Generally, either a single sensor or a plurality of sensors are attached to a device such as a helmet and the position of those sensors is determined relative to known reference points. In an aircraft targeting application, a plurality of sensors are placed in a pilot's helmet and the position of those sensors is determined. Knowing the position of the plurality of sensors, the orientation of the pilot's helmet can be calculated in relation to a reference axis of the aircraft. The orientation of the pilot's helmet can then be used to direct certain devices in the same general direction as the pilot's line of sight.
One prior approach to determining the position and orientation of an object is to utilize magnetic transmitters and receivers. Typically, a magnetic signal is transmitted of a known value from a known reference point. Receivers, or sensors, placed in free space sense the magnetic signal and the position of the receiver is calculated based on the magnitude and direction of the sensed magnetic field signal. The receivers used in this type of application are three axis magnetic sensors which can detect three orthogonal components of a magnetic field.
When these magnetic transmitters and sensors are utilized in an aircraft cockpit, adjustments must be made to account for the large amounts of metal in the area. The presence of a metal object in close proximity to the magnetic transmitter can seriously alter the strength and uniformity of a magnetic field. Since large amounts of metals exist on an aircraft, eddy currents in the metal produce magnetic fields which distort any transmitted magnetic fields at all points in the cockpit. Due to these eddy currents, signals received by the sensor are not true indications of position. These metal effects produce serious errors when trying to determine the position and orientation of sensors within a cockpit.
One solution to the problem of metal effects has been to map the area involved. More specifically, measurements are made in the cockpit wherein a known signal is generated and the sensor is positioned at a known position, resulting in a sensor signal. This sensor signal is then stored and the characteristics of the magnetic field within the entire cockpit are thus determined. Once the magnetic field characteristics are determined, the errors due to metal effects can thus be accounted for.
Another solution to the problem of metal effects is to utilize optical signals rather than magnetic signals. In this application an optical signal is generated from a known point within the cockpit and an optical sensor receives the optical signal. Several disadvantages are inherent in the use of optical signals. One disadvantage is the necessity to have a free path between the sensor and transmitter. Any object placed between the transmitter and the receiver will render the device inoperable and ineffective. Furthermore, the receivers will have a limited field of operation. For example, when an optical signal is placed directly behind the pilot's head and the optical sensor is placed directly on the back of the pilot's helmet, should the pilot turn his head too far the optical signal will not be received. Thus, there is a need for multiple optical sensors and multiple optical signal sources.
SUMMARY OF THE INVENTION
The present invention makes use of magnetic fields to detect the position and orientation of a sensor. Magnetic fields can be projected through certain objects and certain materials, thus do not require a clear path between the transmitter and sensor. Furthermore, magnetic field transmitters and sensors can be better protected through appropriate shielding and protection.
To reduce the metal effects which degrade the accuracy of a system utilizing magnetic fields, the present invention creates a rotating magnetic field vector as its probe signal rather than a uniform magnetic field. This magnetic field vector is rotated at a predefined frequency. A measurement is made of the time period required for the magnetic field vector to pass through a known reference point and the point at which the magnetic field vector encounters the sensors. By knowing the time required for the rotating magnetic field vector to travel between the known reference point and the sensor and by also knowing the frequency of the rotating magnetic field vector, an angle can be determined between a known reference vector and a position vector which extends from the transmitter directly to the sensor.
In the present invention a three-axis magnetic transmitter is utilized, thus allowing the capability of creating rotating magnetic field vectors about three orthogonal axis. By measuring angles with respect to the three orthogonal axis, the position of the sensor can then be determined with reference to the transmitter.
The present invention uses an orthogonal three axis magnetic field sensor. By taking the output from each axis of the three-axis magnetic field sensor and performing a root sum of squares operation upon the three outputs, a signal is created which indicates when the rotating magnetic field vector has encountered the sensor.
The magnetic field sensor is only concerned in determining the time at which the rotating magnetic field vector encounters the sensor. Consequently, the magnetic field sensor is not as concerned with the amplitude or orientation of any magnetic field's detected. By performing a root sum of squares operation upon the three orthogonal outputs, a wave form is generated which indicates the time at which the rotating magnetic field vector encounters the sensor. A root sum of squares signal is utilized because of its sensitivity to amplitudes received and its lesser sensitivity to noise.
Because the present invention is less effected by the magnitude of magnetic field signals which are sensed by the magnetic field sensor, this method of position sensing is less susceptible to metal effects.
By using a plurality of sensors and determining the relative position of each of these sensors with respect to the magnetic field transmitter, the orientation of the sensors can thus be calculated. All of these positions and orientations are calculated based upon relative angles measured. The determination of position and orientation using such angles requires fewer calculations and reduces the complexity of calculations.
It is an object of the present invention to create a device for measuring position and orientation of objects which is less sensitive to eddy currents and metal effects.
It is a further object of the present invention to provide a method of position determination having reduced complexity of calculations and reduced magnitude of calculations.
BRIEF DESCRIPTION OF THE DRAWINGS
Further objects and advantages of the present invention can be seen by reading the following detailed description in conjunction with the drawings in which:
FIG. 1 is a block diagram of the system implementing the present invention;
FIG. 2 is an illustration of the method of the present invention used to determine the position and orientation of the two magnetic field sensors which are attached to a pilot's helmet;
FIG. 3 is a schematic diagram of the signal generator used to drive the magnetic field transmitter of the present invention;
FIG. 4 is a graph showing one scheme to generate the necessary magnetic fields; and
FIG. 5 is a schematic diagram illustrating the circuitry used to detect the magnetic fields and produce a root sum of squares output;
FIG. 6 is a graphical illustration showing the relationship between the signals produced by the magnetic field transmitter and the root sum of squares output; and
FIG. 7 is a block diagram of a second embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a method and apparatus to determine the position and orientation of objects in free space. More specifically, the present invention utilizes a multiple axis magnetic field transmitter in conjunction with a plurality of magnetic sensors to determine the position and orientation of a pilot's helmet with the cockpit of an aircraft. The plurality of sensors are connected to the helmet at a known distance and orientation from one another. By determining the position of each of these sensors, the position and orientation of the helmet can also be determined. This positioning and orientation of the pilot's helmet can then be used to control other devices, such as armaments, vision enhancing devices and navigation equipment.
Referring now to FIG. 1, there is shown a block diagram of a system which implements the concepts of the present invention. The transmission and receipt of magnetic field signals is controlled by a microprocessor or a distributed digital signal processor 10. Microprocessor 10 communicates with a drive signal generator 12 which generates appropriate signals to drive a magnetic field transmitter 20. As seen in FIG. 1, transmitter 20 comprises three orthogonal coils: an X-coil 22, a Y-coil 24, and a Z-coil 26.
Transmitter 20 creates the appropriate rotating magnetic field vectors which are thus received by a first receiver, or sensor, 30 and a second receiver, or sensor, 32. As previously mentioned, first receiver 30 and second receiver 32 are attached to a pilot's helmet 34. These signals received by first receiver 30 and second receiver 32 are transmitted to a first amplifying network 36 and a second amplifying network 38. First amplifying network 36 and second amplifying network 38 produce amplified outputs which are then fed to a first signal processing stage 40 and a second signal processing stage 42, respectively. First signal processing stage 40 has an output which is transmitted back to microprocessor 10. Similarly, second signal processing stage 42 has an output which is also transmitted back to microprocessor 10. Microprocessor 10 can then calculate the appropriate angles for each of the signal sets received. Information regarding position and orientation of first sensor 30 and second sensor 32 and furthermore, position an orientation of the helmet can then be transmitted to peripheral devices from microprocessor 10 via an output 46.
Referring more specifically to drive signal generator 12, all necessary elements are included to allow differing signals to be loaded into a memory and to subsequently drive transmitter 20 consistent with the loaded signals. Microprocessor 10 provides signals to a load and clock logic device 50 which contains the necessary logic to load wave forms into memory or alternatively, to trigger and generate wave forms from memory. Attached to load and clock logic device 50 is an X-memory 52, Y-memory 54 and Z-memory 56. X-memory 52 is capable of storing appropriate signals which will subsequently be transmitted to the X-coil 22 of transmitter 20. Similarly, Y-memory 54 contains the signal to be transmitted to the Y-coil 24 and Z-memory 56 contains the signals to be transmitted to the Z-coil 26. Attached to an output of X-memory 52 is a digital to analog (D to A) converter 58. Similarly, connected to the output of Y-memory 54 is a second digital to analog (D to A) converter 60. Lastly, connected to an output of Z-memory 56 is a third digital to analog (D to A) converter 62. First D to A converter 58, second D to A converter 60, and third D to A converter 62 are all used to convert signals stored in their attached memories to an analog signal. The output of first D to A converter 58 is transmitted to a first input of a first multiplying D to A converter 64. Second D to A converter 60 is connected to second multiplying D to A converter 66 and third D to A converter 62 is connected to third multiplying D to A converter 68. Each multiplying D to A converter 64, 66 and 68 have a second input 70, 72 and 74, which are all connected to microprocessor 10. These D to A second inputs 70, 72 and 74, allow the microprocessor to dynamically adjust the magnitude of these signals being transmitted to each of the coils of transmitter 20. This adjustment is necessary due to non-uniformity to the three orthogonal coils in transmitter 20 and to adjust gain as a function of the separation between transmitter 20 and receiver (either first receiver 30 or second receiver 32). Multiplying D to A converter 64 has an output which is connected to an X-drive amplifier 78. X-drive amplifier 78 provides the necessary amplification and current necessary to drive the X-coil 22 of transmitter 20. Similarly, second multiplying D to A converter 66 has an output connected to a Y-drive amplifier 80 which is used to drive the Y-coil 24 of transmitter 20. Lastly, third multiplying D to A converter has an output which is attached to a Z-drive amplifier 82 which provides the necessary amplification to drive the Z-coil 26 of transmitter 20. Attached to the output of X-drive amplifier 78 is a sampling connection 84 connected to microprocessor 10. Sampling connection 84 is used to transmit a reference signal to microprocessor 10. It will be understood by those skilled in the art that sampling connection 84 could be connected to the output of Y-drive amplifier 80 or the output of Z-drive amplifier 82, or any combination thereof.
As previously mentioned, transmitter 20 has three separate coils arranged orthogonally. These coils can be separately energized to create a magnetic field having the desired characteristics. Referring now to FIG. 4, there are shown appropriate wave forms to create the desired rotating magnetic field vector. This illustration graphically shows the wave forms directed to each orthogonal coil, thus resulting in a rotating magnetic field vector.
Shown at time period t 1 are the necessary drive signals to create a rotating magnetic field vector which will rotate about the Z-axis. As shown in FIG. 4, X-drive amplifier 78 outputs a sinusoidal signal 90 while Y-drive amplifier 80 outputs a second sinusoidal signal 92. By having X-sinusoidal signal 90 an Y-sinusoidal 92 phased 90 degrees apart, the resulting magnetic field vector 94 will rotate in free space around the Z-axis.
During time period t 2 , Y-drive amplifier 80 outputs a similar sinusoidal signal 92 to the Y-coil 24, while Z-coil amplifier 82 outputs a Z-sinusoidal signal 96. During time period t 2 , Y-sinusoidal signal 92 and Z-sinusoidal signal 96 are phased 90 degrees apart, again resulting in a rotating magnetic field vector 94 which will rotate about the X-axis. Lastly, during time period t 3 X-drive amplifier 78 outputs X-sinusoidal signal 90 to X-coil 22 while Z-drive amplifier 82 outputs Z-sinusoidal signal 96 to Z coil 26. During time period t 3 , Z-sinusoidal signal 96 and X sinusoidal signal 90 are arranged to be phased 90 degrees apart, again resulting in magnetic field vector 94 to rotate about the Y-axis.
In summary, by applying the correct voltage signals to X-coil 22, Y-coil 24 and Z-coil 26, a magnetic field vector can be obtained which will rotate about the appropriate axis. It is important to note that the X-sinusoidal signal 90, Y-sinusoidal signal 92 and Z-sinusoidal signal 96 are all of the same frequency, thus creating a magnetic field vector that will rotate at that same frequency. By holding this frequency constant it is known that magnetic field vector 94 will rotate a certain amount in a given period of time.
Referring now to FIGS. 2a, 2b and 2c, there is shown a graphical illustration which helps to explain how the measured angles are used to determine the position in orientation of a pilot's helmet. As shown in FIG. 2a, transmitter 20 is positioned at a known reference point and oriented along an X and Y-axis. By appropriately driving X-coil 22 and Y-coil 24, a rotating magnetic field vector is created which rotates about the Z-axis (into the page). Shown in FIG. 2a, rotating magnetic field vector 94 rotates in a clockwise direction. The positive Y-axis is arbitrarily chosen as a reference point and the time required for rotating magnetic field vector 94 to travel between the Y-axis and first sensor 30 is measured. Similarly, the time required for rotating magnetic field vector 94 to travel between the Y-axis and second sensor 32 is also measured. From these time measurements and the frequency of rotating magnetic field vector 94, angles θ 1 and θ 2 can be determined.
FIG. 2b shows a similar diagram having rotating magnetic field vector 94 rotating about the Y-axis. In FIG. 2b rotating magnetic field vector is shown to rotate in a counterclockwise direction. Here the X-axis is chosen as a reference point and the time required for rotating magnetic field vector 94 to travel between reference X-axis and first sensor 30 is determined. Similarly, the time required for rotating magnetic field vector to travel between reference X-axis and second sensor 32 is also determined. Again, from these time measurements and the frequency of rotating magnetic field vector 94, the angles φ 1 and φ 2 can be determined.
Lastly, FIG. 2c illustrates the rotating magnetic field vector 94 traveling in a counter clockwise direction around the X-axis. Here the Y-axis is chosen as a reference and the time period required for rotating magnetic field vector 94 to travel between the Y-axis and first sensor 30 is measured. Similarly, the time required for rotating magnetic field vector 94 to travel between the Y-axis and second sensor 32 is also measured. From these time measurements, the angles β 1 and β 2 can be determined.
As will be recognized by those skilled in the art, once all of the necessary angles are measured the position with reference to transmitter 20 of first sensor 30 and second sensor 32 can easily be determined. It will be noted that there are many methods of determining this position, all of which shall function equally as well. Thus, a position of first sensor 30 having coordinates X1, Y1, Z1 and the position of second sensor 32 having coordinates X2, Y2 and Z2 are known. By knowing the distance and orientation of the sensors 30 and 32 with respect to one another, the position and orientation of the helmet can then be determined.
It will be further recognized that the position and orientation of a pilot's helmet can also be determined using different combinations of hardware. One alternate embodiment of the present invention utilizes three receivers attached to the pilot's helmet and utilizes only two rotating magnetic field vectors. Transmitter 30 is driven by microprocessor 10 which allows the capability to generate many different types of magnetic signals, including rotating magnetic field vectors in either two or three axes.
Referring now to FIG. 3, there is shown a more detailed schematic diagram of drive signal generator 12. Drive signal generator 12 receives numerous signals from microprocessor 10. Specifically, drive signal generator 12 receives a data signal 100, a clock signal 102, and an address signal 104. These inputs (data line 100, clock signal 102, and address line 104) allow microprocessor 10 to load particular waveforms into signal generator memory and to trigger those waveforms, resulting in the generation of appropriate signals being sent to the three coils 22, 24 and 26 of transmitter 20.
Load and clock logic device 50 contains a first latch 108 and a second latch 110. The use of two latches allows data received on data line 100 (which is 8 bits wide) to be combined to provide a 12 bit data signal out of a combination of first latch 108 and second latch 110. The data output from the two latches, 108 and 110, is then transmitted to either X-memory 52, Y-memory 54 or Z-memory 56.
Signals received on generator address line 104 are input to a programmable array logic device (PAL) 112. First PAL 112 is used for address steering to direct signals to the correct memory blocks.
Clock signal 102 is input to a second PAL 114. Second PAL, in conjunction with a third PAL 116, is used to coordinate the timing of data transfers.
Shown in FIG. 3, X-memory 52 contains two 8 bit memory blocks, a first X-memory block 120 and a second X-memory block 122. Similarly, Y-memory 54 contains a first Y-memory block 124 and a second Y-memory block 126; and lastly, Z-memory 56 contains a first Z-memory block 128 and a second Z-memory block 130.
X-memory 52, Y-memory 54 and Z-memory 56 all contain two individual memory blocks to allow the handling of 12 bits of data while utilizing 8 bit memory devices. Each of the memory blocks, 120, 122, 124, 126, 128 and 130 all have the necessary data lines and addressing lines attached thereto to allow manipulation of 12 bits of data.
X-memory 52 outputs a signal to first D to A converter 58. Similarly, Y-memory 54 outputs to second D to A converter 60 while Z-memory 56 outputs to third D to A converter 62. Each of these D to A converters 58, 60, 62 are used to convert the digital signals stored in memory to analog signals. The appropriate analog signal is then output to a subsequent device.
The first D to A converter 58 outputs its analog output to an X-buffer amplifier 134, which then transmits the analog signal to first multiplying D to A converter 64. Similarly, the second D to A converter 60 has its analog output connected to a Y-buffer amplifier 136 which then transmits an analog signal to second D to A converter 66. Lastly, the third D to A converter 62 has its output connected to a Z-buffer amplifier 138 which then transmits an analog signal to third multiplying D to A converter 68.
First multiplying D to A converter 64 receives the analog signal from X-buffer amplifier 34 along with an address signal from first PAL 112 and a data signal from first latch 108 and second latch 110. The address signal from PAL 112 and the data signal from latches 108 and 110 allow microprocessor 10 to adjust the level of analog signals being transmitted from X-buffer amplifier 134. This allows the first multiplying D to A converter 64 to dynamically adjust its output as necessary.
First multiplying D to A converter 64 supplies its output to X-drive amplifier 78. X-drive amplifier 78 consists of an operational amplifier and power driver 140 having its output connected to X-coil 22. Also connected at the output of operational amplifier 140 is a filtering configuration having a first capacitor 142 and a resistor 144. Capacitor 142 and resistor 144 are connected in a negative feedback configuration to allow appropriate filtering of operational amplifier 140 output. Also connected in series with X-coil 22 is a second filtering capacitor 146 in conjunction with a load resistor 148.
Second multiplying D to A converter 66 and third multiplying D to A converter 68 are configured the same as first multiplying D to A converter 64. Their outputs are connected to Y-drive amplifier 80 and B drive amplifier 82, respectively. Y-drive amplifier 80 and Z-drive amplifier 82 are configured similarly to that of X-drive amplifier 78.
Referring now to FIG. 5, shown in a more detailed schematic diagram of first amplifying network 36 or second amplifying network 38 as well as first signal processing stage 40 or second signal processing stage 42.
Both first sensor 30 and second sensor 32 have three orthogonally configured coils which are particularly sensitive to magnetic fields aligned along each orthogonal axis. The axis of sensitivity of each coil is conveniently referred to as the X-axis, Y-axis and Z-axis. Each coil has two outputs to which sensing devices can be attached. The X-coils of the first sensor 30 are attached to two input terminals 160 and 162 of an X-pickoff amplifier 164. X-pickoff amplifier 164 is configured to sense the amount of current induced in the X-sensor coil 152.
Connected at the output of X-pickoff amplifier 164 is a first filter capacitor 170 and a first filter resistor 172. The output from first filter capacitor 170 is then fed into an X-analog multiplier 176. X-analog multiplier is configured to output an analog signal equal to the square of the signal present at its input. In the present embodiment analog multiplier is an analog device AD534. The output from X-analog multiplier 176 is then fed into a summing amplifier 180.
First amplifying network 36 also has two inputs, 184 and 186, connected to the Y-sensor coil 154 as well as two inputs, 188 and 190, connected to the Z-sensor coil. Y-high input 184 and Y-low input 186 are connected to a Y-pickoff amplifier 192 which then outputs a voltage signal indicative of the current induced in Y-sensor coil 154. Similarly, a Z-pickoff amplifier 194 is connected to Z-high input 188 and Z-low input 190 to output a signal indicative of the amount of current induced in Z-sensor coil 156. The output from Y-pickoff amplifier 192 is fed through a filter capacitor 170 and filter resistor 172 and input to a Y-analog multiplier 196. Similarly, the output from Z-pickoff amplifier 194 is fed into a filter capacitor 170 and a filter resistor 172. The output from filter capacitor 170 is then fed into a Z-analog multiplier 198. Y-analog multiplier 196 and Z-analog multiplier 198 are configured similarly to that of X-analog multiplier 176 to provide an output which is equivalent to the square of the analog voltage signal received at its input. The output from Y-analog multiplier 196 is fed to a second input of summing amplifier 180. Similarly, the output of Z-analog multiplier 198 is fed to a third input of summing amplifier 180.
Summing amplifier 180 is configured in a well known configuration to provide an analog output voltage equal to the inverse of the sum of the analog input voltages. The output of summing amplifier 180 is connected to inverting amplifier 200. Inverting amplifier 200 is configured to provide an output signal that is equivalent in magnitude to its input signal; however, having an inverse polarity.
The output of inverting amplifier 200 is then fed to the input of an analog multiplier 202. Analog multiplier 202 is configured to provide an output which is equal to the square root of the analog signal received at its input. The output of analog multiplier 202, or square root multiplier 202, is connected to a buffer amplifier 206 which has its output connected to a second filter capacitor 208. Connected at the output of filter capacitor 208 is a second resistor 210. Also connected at the output of second capacitor 208 is a gain amplifier 212. Gain amplifier 212 is configured to provide signal conditioning amplification necessary at the output stage.
The schematic diagram shown in FIG. 5 illustrates the circuitry necessary to process signals from one sensor. For example, the circuitry shown in FIG. 5 may be connected to first sensor 30 and as such, makes up portion of first amplifying network 36 and first signal processing stage 40. It is understood that second amplifying network 38 and second signal processing stage 42 are identical to first amplifying network 36 and first signal processing stage 40.
To summarize the operation of first amplifying network 36 and first signal processing 40 it is beneficial to trace through the functionality of each block. At the input of X-analog multiplier 176 the analog voltage level is indicative of the X component of a sensed magnetic field (an X-magnitude signal). At the output of first analog multiplier 176, the analog signal voltage is equivalent to the square of the X-magnitude signal. Similarly, the output of Y-analog multiplier 196 is equivalent to the square of a Y-magnitude signal and the output of Z-analog multiplier 198 has a magnitude equivalent to the square of a Z-magnitude signal. These signals are then input to summing amplifier 180 and inverting amplifier 200 to result in a signal equivalent to X squared plus Y squared plus Z squared (X 2 +Y 2 +Z 2 ). By inputting this signal into analog multiplier 202 results in a signal equivalent to the square root of X squared plus Y squared plus Z squared (the root sum of squares, or RSS signal) ##EQU1## .
This signal is then available at the output of gain amplifier 212 with its DC component removed by filter network 208 and 210.
The root sum of squares signal was utilized to indicate the time at which rotating magnetic field vector 94 is encountered by first sensor 30. The root sum of squares signal (RSS signal) does not depend upon the orientation of the sensor while still being a good indicator of the presence of rotating magnetic field vector 94. This signal can then be input to microprocessor 10 for detection of the peak of the RSS signal to indicate the time at which rotating magnetic field vector encounters first sensor 30. Detection of the rotating magnetic field vector 94 by second sensor 32 is similarly accomplished.
In the present embodiment, the RSS signal is created by utilizing numerous analog components. It will be understood that an equivalent signal could be created using other methods such as a digital signal processor or a microprocessor.
Referring now to FIGS. 6a, 6b and 6c, there are shown example waveforms which illustrate the signal relationships of the present invention. FIG. 6a illustrates the appropriate waveforms when a sensor is placed at a 45 degree angle with respect to transmitter 20 while being in the same plane. As shown in FIG. 6a, the X-coil receives a sinusoidal signal 220 while the Y-coil receives a similar sinusoidal signal 222 which is out of phase with X-signal 220. These two signals create a rotating magnetic field vector which rotates in a clockwise direction. Note that the signal received by Z-coil 224 is zero. An output signal 226 received from the signal processing network shown on FIG. 5 is illustrated with its DC component present. This signal is a root sum of squares signal received from the three sensor coils. As can be shown in FIG. 6a, the RSS signal 226 peaks at a time 45 degrees from the reference point where Y equals 0 and X equals 1.
Referring now to FIG. 6b, there is shown an illustration of appropriate waveform when the sensor is positioned directly on the X-axis. Here the reference point is chosen to be the point at which the magnetic field vector is pointing along the negative Y-axis. Here the RSS signal 226 peaks at a time equivalent to a 90 degree angle. This is consistent with what would be expected.
Referring to FIG. 6c there is shown an illustration which relates the appropriate wave forms when the sensor is positioned on the negative Y-axis. Here the reference point is chosen to be time at which the magnetic field vector 94 is direct along the positive Y-axis and the magnetic field vector 94 rotates in a clockwise direction. Note that the RSS signal 226 peaks at a time equivalent to 180 degrees.
Referring to FIG. 7, there is shown an alternative embodiment of the present invention. This embodiment utilizes the principles previously described; however, provides the enhancement of utilizing a multiple frequency magnetic field. (Elements remaining the same as those depicted in FIG. 1 have maintained their same reference numbers.) Again, microprocessor 10 provides a number of signals to drive signal generator 12. These signals provide drive signal generator 12 with the ability to drive the three coils (X-coil 22, Y-coil 24, and Z-coil 26) of transmitter 20. However, in this embodiment, drive signal generator 12 is loaded with drive signals containing two frequency components. Transmitter 20 would be driven by a composite signal having one low frequency component and one high frequency component. Driving the transmitter in such a way again creates rotating magnetic field vectors; however, one magnetic field vector rotates at a high frequency while a second rotating magnetic field vector rotates at a low frequency. In this embodiment, the low frequency component of the transmitter drive signal would be below the level of eddy current effects (from 30 to 100 hertz), thus eliminating some of the metal effects within a cockpit. A second component of the composite signal would run at approximately 11 Khz. The idea of using a multiple frequency transmitter signal and rotating magnetic field vectors of multiple frequencies is to continuously update the position and orientation of the receivers 30 and 32 at a very high frequency (11 Khz) while correcting the high frequency updates periodically for eddy current effects. The low frequency component is below the level at which eddy current effects create errors, thus will provide an accurate measure of position.
In order to accomplish the goal of using multiple frequency components, the signal processing and signal conditioning must be altered slightly. First receiver 30 and second receiver 32, again, sense magnetic fields which are generated by transmitter 20. These signals are then transmitted to a first amplifying network 36 and a second amplifying network 38. However, the outputs of first amplifying network 36 and second amplifying network 38 are connected to a first filtering network 230 and a second filtering network 232 for purposes of separating the different frequency components of the received signals. First filtering network 230 provides a high frequency output to a first high frequency processing stage 240, while second filtering network 232 provides a high frequency output to second high frequency processing stage 242. Similarly, first filtering network 230 provides a low frequency output to first low frequency processing 244, while second filtering network 232 provides a low frequency to second low frequency processing stage 246. All of the processing stages (first high frequency processing stage 240, second high frequency processing stage 242, first low frequency processing stage 244 and second low frequency processing stage 246) provide the necessary circuitry or processing to develop an RSS signal from the signal sensed by first receiver 30 and second receiver 32. These RSS signals are then communicated to processor 10.
While it is shown that separate processing stages are used for each frequency component of the received signals, it will be understood by those skilled in the art that numerous methods to achieve this goal exist. For example, signals could be multiplexed into a signal processing stage, or all signal processing could be carried out by a digital signal processor.
Note that other alterations may be necessary to implement this second embodiment. Specifically, filtering network 42 and 44 must be removed from the output stage of drive amplifying 78, 80 and 82. Similar filtering aspects must be similarly accounted for throughout the circuitry.
Having described the present invention in considerable detail, it is understood that certain modifications can be made to the specific detail described. We claim all modifications coming within the scope and spirit of the following claims. | A method of measuring the position and orientation of an object is disclosed in conjunction with an apparatus to achieve this method. The method and apparatus reduce the metal effects caused by metal objects which are in close proximity to a magnetic field generator. The metal effects are reduced by utilizing a magnetic field generator which creates a rotating magnetic field vector and then measuring the time required for that magnetic field vector to travel between a known reference point and the sensor whose position is being measured. By keeping the frequency of the rotating magnetic field vector constant and measuring the time required for this magnetic field vector to travel the previously mentioned distance, an angle between a reference axis and a vector directed toward the sensor can be determined. Once appropriate angles are measured, calculations can be undergone to determine the position of the sensor. Furthermore, by utilizing a plurality of sensors the orientation of the sensors with respect to one another can be determined. | 6 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to new and useful improvements in ear jewelry and more particularly pertains to a new and improved earring construction for pierced ears which includes the use of a rotatable head attached to the stem portion of an earring or the like, whereby the stem may be inserted through a wearer's ear and the rotatable head may then be moved into a position which prevents the stem, and thus the earring, from becoming disengaged from the wearer's ear, thereby to eliminate the need for a separate retaining fastener.
2. Description of the Prior Art
Piercing type earrings having stems or posts designed to pass through openings in earlobes are well known in the art. These earrings normally require the use of separable fasteners or clips that are attachable to end portions of the posts after the posts have been inserted through earlobe openings, thereby to prevent accidental withdrawal of the posts which could result in earring loss. With respect to piercing type earrings, it can be appreciated that substantial problems have been encountered in attempting to design fasteners which won't inadvertently become separated from the earring posts whereby a loss of the associated earring could result. This problem is particularly troublesome when an earring is made of a precious metal or is provided with precious stones inasmuch as a loss of the earring could result in considerable financial deprivation.
There have been several attempts to overcome the problem of losing earrings as a result of an inadvertent disengagement of associated fasteners. For example, U.S. Pat. No. 3,260,068, which issued to Arthur Micallef on July 12, 1966, and U.S. Pat. No. 3,446,033, which issued to Jesse Driscoll on May 27, 1969, both disclose earrings for pierced ears wherein the earrings include stems bent in a manner which effects a retaining of the associated earring in an earlobe without the necessity of utilizing a separate fastener on the stem. More particularly, both of these earring constructions rely upon the substantially transverse positioning of an angulated end portion of a stem with respect to an earlobe, thus to effect a frictional gripping action as occasioned by the attendant weight of the associated earring. While these designs may eliminate the need for a separable fastener, it can be appreciated that substantial difficulty and pain may be experienced in forcing these bent stems through an earlobe, while at the same time there still exists the possibility that the stems could become undesirably disengaged.
A different manner of attaching a single piece earring to an earlobe is disclosed in U.S. Pat. No. 3,446,034, which issued to Jesse Driscoll on May 27, 1969, wherein a complexly-designed attaching means is employed. In this patent, a hollow earring stem is designed to be inserted completely through an earlobe, while a flexible line extends partially through the hollow stem so as to extend out of one end thereof and also out of a separate opening centrally positioned on the stem. A pair of ornaments are attached to respective ends of the flexible line, with the post being positioned transverse to the earlobe after being inserted therethrough while both ends of the flexible line will extend through the earlobe opening. While tending to possibly retain an earring more securely than the above-discussed bent post constructions, it can be appreciated that this form of attaching means is complex to manufacture, requires that the ornaments be retained on flexible lines, and could also cause ear irritation due to the use of the pair of flexible lines through the earlobe opening as opposed to a smooth gold-plated earring post.
Accordingly, it is apparent that there exists a continuing need for improved pierced ear jewelry which eliminates the possibility of loss of separable fasteners while at the same time permitting a quick, secure and comfortable attachment of the associated earring to an earlobe. In this respect, the present invention substantially fulfills this need.
SUMMARY OF THE INVENTION
The general purpose of the present invention, which will be described subsequently in greater detail, is to provide new and improved pierced ear jewelry which has all of the advantages of the prior art pierced ear jewelry and none of the disadvantages. To attain this, the present invention envisions the use of an earring having a modified stem portion which includes an axially aligned slot. Rotatably secured within the stem slot is an elongate head portion whereby the head portion may be rotated into axial alignment with the slot, thus to present a stem which is easily inserted through an earlobe. After insertion through an earlobe, the head portion may be rotated into a transverse orthogonal relationship with the stem thus to effect a desired retention of the associated earring within the earlobe without the necessity of utilizing a separable fastener.
It is therefore an object of the present invention to provide new and improved pierced ear jewelry which has all of the advantages of the prior art pierced ear jewelry and none of the disadvantages.
It is another object of the present invention to provide new and improved pierced ear jewelry which may be easily and efficiently manufactured.
It is a further object of the present invention to provide new and improved pierced ear jewelry which may be securely and comfortably attached to earlobes.
Even another object of the present invention is to provide new and improved pierced ear jewelry having a reliable loss-preventing attaching means.
Still another object of the present invention is to provide new and improved pierced ear jewelry which eliminates the need for separable fasteners, thus to lessen the likelihood of loss of an associated earring.
An even further object of the present invention is to provide new and improved pierced ear jewelry which is susceptible of a low cost of manufacture with regard to both materials and labor, and which accordingly is then susceptible of low prices of sale to the consuming public, thereby making such earrings economically available to the buying public.
Still yet another object of the present invention to provide new and improved pierced ear jewelry which provides in the apparatuses and methods of the prior art some of the advantages thereof, while simultaneously overcoming some of the disadvantages normally associated therewith.
These together with other objects of the invention, along with the various features of novelty which characterize the invention, are pointed out with particularity in the claims annexed to and forming a part of this disclosure. For a better understanding of the invention, its operating advantages and the specific objects attained by its uses, reference should be had to the accompanying drawings and descriptive matter in which there are illustrated preferred embodiments of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a piercing-type earring forming the present invention operably attached to a wearer's earlobe.
FIG. 2 is a cross-sectional plan view taken along the line 2--2 in FIG. 1.
FIG. 3 is an enlarged detail view, partly in cross-section, which more particularly illustrates the manner of attachment of the present invention to an earlobe.
FIG. 4 is a top plan view, partly in cross-section, taken along the line 4--4 in FIG. 3.
FIG. 5 is a perspective view of a modified embodiment of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
With reference now to the drawings and in particular to FIGS. 1 and 2 thereof, a new and improved piercing type ear jewelry embodying the principles and concepts of the present invention and generally designated by the reference numeral 10 will be described. In this respect, it can be seen that the ear jewelry 10 may include an ornament portion 12 and an attachment stem or post 14 integrally or otherwise fixedly secured to the ornament portion. The stem 14 is designed to be inserted through a pierced opening 16 formed within a wearer's earlobe 18. With respect to the ornament portion 12, it is to be understood that the ring-like construction of the ornament portion illustrated in the drawings is only representative of virtually any conceivable configuration and design of ornament which may be employed in ear jewelry, to include the use of precious stones, metals, and the like. Accordingly, all such configurations and designs are within the purview of the described invention.
The attachment post 14 further includes a novel retaining means 20 which operates to prevent the disengagement of the post from the earlobe 18 after the post has been inserted through the opening 16.
As shown in FIGS. 3 and 4, the post 14 may include an elongate through-extending slot 22 extending over a partial axial length of the post and a rotatable head member 24 fixedly retained within the slot. As illustrated, the head member 24 is rotatable about a shaft 26 positioned within the slot 22 and extending between and through a pair of respective sidewalls 28, 30 forming a part of the post 14. The shaft 26 may be fixedly secured within the slot 22 between the sidewalls 28, 30 by any known conventional means, to include threadable attachment, welding, etc.
Also shown in FIG. 3 is the use of an optional bulbous end formed on an end portion of the post 14 and more particularly as a part of the respective sidewalls 28, 30. In this regard, the bulbous head portion 32 facilitates a spreading of the earlobe opening 16 during an insertion of the post 14 therethrough, thus to prevent any undesired discomfort which might otherwise be experienced as a result of the wearer's earlobe becoming undesirably pinched or otherwise engaged with the slot 22 during post insertion. Further, the spreading of the earlobe aperture 16 by the bulbous end member 32 also substantially eliminates any possibility of an undesired rotation of the head member 24 within the slot 22 prior to the complete insertion of the stem 14 through the earlobe 18, where such rotation of the head member might be otherwise occasioned by the frictional resistance of the earlobe if the earlobe opening was not sufficiently spread apart.
FIGS. 3 and 4 also illustrate the use of an expanded rim 34 on the ornament 12, such rim being integrally or otherwise fixedly secured thereto, with the purpose of the rim being to limit the depth of insertion of the post 14 within the earlobe opening 16. Inasmuch as a pierced earring post 14 desirably requires a plating with some precious metal, such as gold or the like, to thereby prevent infection and other possible ear irritation or discomfort, the use of the rim 34 limits the depth of penetration of the post 14 thus to effectively determine the amount of precious metal plating which needs to be applied to a post. Further, the rim 34 helps to facilitate a stable retention of the ear jewelry 10 in position in an earlobe 18, as well as to desirably retain the ear jewelry in a stable decorative position.
FIG. 5 illustrates an alternative embodiment of the present invention wherein the rotatable head member 24 is provided with an axially-extending, elongate slot 36. With respect to this further embodiment of the invention 10, the shaft 26 extending across the slot 22 also extends through the slot 36 in the head member 24. In this connection, the shaft 26 is slidably retained within the slot 36 whereby axial movement of the head member 24 with respect to the shaft 26 is afforded. This construction then permits the head member 24 to be axially aligned with the post 14 and to be substantially slid back into the slot 22 during an insertion of the post 14 through an earlobe opening 16. After a completed insertion of the post 14 through an earlobe opening 16, a wearer may then grasp the head member 24 and pull it in an axial direction outwardly from the slot 22 prior to rotating the head member into an orthogonal locking position as shown in FIG. 5. This construction then increases the ease and efficiency of attaching an earring 10 to an earlobe 18.
A further feature illustrated in the embodiment of the invention shown in FIG. 5 is the redesigning of the slot 22. More particularly, rather than cut the slot 22 completely through the post 14, one end of the slot may be cut only partially through the post whereby a blocking surface 38 is created within the slot. This construction then limits the extent of rotation of the head member 24 whereby once the head member is rotated in a clockwise manner into the slot 22, it will abut against the blocking surface 38 and be prevented from continued movement in a clockwise direction. A counterclockwise rotation of the head member 24 will then bring the same into the transverse locking position as shown in FIG. 5, while a lower portion 40 of the blocking surface 38 will effectively prevent continued counterclockwise rotation of the head member out of its locking position
In use then, it can be appreciated that with respect to both embodiments of the invention, a wearer of a particular earring 10 need only to axially align the head member 24 with the post 14, so that the head member is substantially completely retained within the slot 22, and then insert the post through the earlobe opening 16. The bulbous end member 32 will effect a desired spreading of the earlobe opening 16 so that no binding or discomfort occurs during the insertion, and after the insertion of the post has been completed, the wearer may grasp the head member 24 and rotate it into orthogonal alignment with the post 14, thus to effect a desired retaining of the post and its associated ornament 12 in position within an earlobe 18. To remove an earring 10, just the opposite procedure is followed, i.e., the head member 24 is rotated back into axial alignment with the post 14 so as to be substantially again retained within the slot 22, whereby the post may be comfortably and quickly disengaged from the earlobe 18.
While a preferred embodiment of the invention has been described, it is to be understood that various other modifications are within the purview of this invention, to include such features as including a second bulbous member at the opposed end of the slot 22, thereby to effect a spreading of the earlobe opening 16 during a disengagement of the earring 10 from the earlobe 18. Further, various locking means could be employed to retain the head member 24 in both its orthogonal and axially aligned positions, to include roughened gripping surfaces, selectively positioned detent and ball arrangements, spring biasing means, etc. With respect to the above-description then, it should be realized that the optimum dimensional relationships for the parts of the invention, 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 the present invention.
Therefore, the foregoing is considered as illustrative only of the principles of the invention. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation shown and described, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope of the invention. | An earring includes a stem or post to be inserted through a pierced ear and an elongated head portion rotatably attached to the end of the stem. The stem is provided with an elongate slot in which the rotatable head portion is retained. During an insertion of the stem through a wearer's ear, the head portion is axially aligned with and substantially retained within the slot. After insertion, the head portion is rotatable into a position transverse to the longitudinal axis of the stem so as to effectively retain the earring in the wearer's ear without the necessity of utilizing a separate conventional fastener. | 8 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional application of U.S. patent application Ser. No. 11/430,364, filed May 9, 2006, the entire contents of which are incorporated herein by reference.
[0002] U.S. patent application Ser. No. 11/430,364 claims priority to U.K. Patent Application No. 0509465.1, filed May 10, 2005, which is incorporated by reference in its entirety.
BACKGROUND
[0003] The present invention relates to a downhole tool for, and a method of, generating a drive force in a downhole environment. In particular, but not exclusively, the present invention relates to downhole tools for generating rotary and axial drive forces in a downhole environment.
[0004] Tools for generating a drive force in a downhole environment are known in the oil/gas industry. These include downhole motors, turbines and setting tools. Turbines are fluid driven and are run on a string of tubing, with associated fluid circulation apparatus at surface. Whilst this is an effective procedure for most drilling applications, it is time-consuming and expensive for secondary drilling applications, such as removing an obstruction in a borehole or de-scaling and hydrate removal procedures.
[0005] Setting tools are used to generate a force to set tools such as plugs, packers and the like, which are initiated by a tensile/compressive load. One known setting tool is the pyrotechnic setting tool which generates high forces by ignition/detonation of a pyrotechnic charge. The pyrotechnic charge is housed in a pressure-tight piston chamber, and detonation generates a controlled burn, releasing gases which generate significant pressure in the chamber. This pressure acts on a piston which Astrokes@, generating a high force, similar to a hydraulic ram, and this force is applied directly to the tool to be set. There are many disadvantages associated with pyrotechnic tools. For example, pyrotechnic charges are require delicate handling under very stringent regulations. Export/import of explosives into and out of certain regions of the world is prohibited. Use of the tool involves significant risks to personnel and structures. An electrical charge is required to ignite or detonate the charge and this limits use of the tool mainly to electric wireline applications. In such applications, radio silence must be enforced in the vicinity of the setting tool during deployment. If the setting tool is deployed on slick wireline, a battery operated trigger or detonator is required which operates on a timer basis, limiting its uses. Finally, failure of the charge to properly detonate creates a significant handling problem.
SUMMARY
[0006] According to a first aspect of the present invention, there is provided a downhole tool for generating a drive force in a downhole environment, the tool including: a chamber for storing a reactant; activating means for activating the reactant; and isolation means for isolating the activating means from the reactant, and for selectively exposing the activating means to the reactant to activate the reactant and generate a drive medium for driving a drive member to generate the drive force.
[0007] Advantageously, this provides a downhole tool which may be used to generate a drive force when required, by exposing the activating means to the reactant. The tool may therefore be located downhole before activating the reactant to generate the drive force, for carrying out a desired downhole procedure. Furthermore, the tool can be easily pulled out of hole for replenishment of the reactant or replacement of the activating means.
[0008] The downhole tool may be, for example, a setting tool; a fishing tool; a cutting tool such as a casing or tubing cutter, a mill, a drill, or a tubing/casing clean-up or de-scaling and hydrate removal tool; a wireline or coiled tubing tractor; or an artificial lift tool for driving a pump.
[0009] Preferably, at least part of the isolation means is movable to expose the activating means to the reactant. In particular, at least part of the isolation means may be moveable between at least an isolation position where a barrier is defined between the activating means and the reactant, and an exposed position, where the activating means is exposed to the reactant. The isolation means may include a movable member and may further include a seal for isolating the activating means from the reactant. The seal may be fixed relative to a body of the tool and the activating means may be coupled to the movable member for moving the activating means into the reactant chamber. Alternatively, the seal may be movable relative to the movable member and the movable member may be movable to release the seal and expose the activating means to the reactant.
[0010] Conveniently, the downhole tool is a one-shot tool for use downhole and subsequent return to surface for replenishment of the reactant and/or the activating means. Alternatively, the downhole tool may be a multi-shot tool; this may allow a number of downhole procedures to be carried out before the tool is required to be returned to surface for replenishment. It will be understood that this may be achieved by selectively isolating and exposing the activating means a number of times downhole.
[0011] Preferably, the downhole tool includes the drive member. The drive member may comprise a rotatable drive member or a member for generating an axial force such as a piston. The rotatable member may in particular comprise a turbine rotor, or a rotor of a motor, such as a positive displacement motor (PDM). Alternatively, the drive member may be separate from the downhole tool, and may form part of a secondary tool.
[0012] Preferably, the reactant comprises a chemical reactant such as an oxidising agent, in particular hydrogen peroxide (H 2 O 2 ), and the activating means comprises catalyst means such as a copper, iron or other metal based catalyst. In particular, the catalyst means may comprise copper or iron sulphate. Thus when the copper/iron based catalyst is exposed to the hydrogen peroxide, the drive medium generated comprises oxygen, and water in the form of steam as the reaction is exothermic. Accordingly, the generated drive medium may comprise a fluid, in particular a gas, liquid, or vapour.
[0013] The movable part of the isolation means may be moveable in response to an applied external force, which may be generally axially directed. The movable part of the isolation means may be directly or indirectly moveable; in particular, it may be adapted to be moved relative to a body of the tool by a force exerted directly on the moveable part. Alternatively, the movable part may be adapted to be moved relative to the body by a force exerted on the tool body. The drive member itself may define the moveable part of the isolation means, and the activating means may be coupled to the drive member, such that movement of the drive member moveable exposes the activating means to the reactant. Alternatively, the moveable part of the isolation means may be moveable by application of a fluid pressure force.
[0014] The tool may be adapted to be run on, in particular, wireline or coil tubing for ease and speed of deployment. However, the tool may be adapted to be run on any suitable means such as drill or completion tubing or the like.
[0015] The downhole tool may include a vent for venting spent drive medium out of the tool. The downhole tool may further comprise a pressure relief valve for controlling the venting of spent drive medium from the downhole tool in the event of the pressure of the drive medium reaching a determined threshold value.
[0016] According to a second aspect of the present invention, there is provided a downhole tool for generating a rotary drive force, the tool having: a chamber for storing a reactant; activating means for activating the reactant; isolation means for isolating the activating means from the reactant, and for selectively exposing the activating means to the reactant to activate the reactant and generate a drive medium; and a rotatable drive member adapted to be driven by the drive medium to generate the rotary drive force.
[0017] Preferably, the downhole tool is a turbine or a motor, such as a positive displacement motor (PDM). Advantageously, the invention provides a turbine or motor, which does not require a motive fluid to be supplied from surface. Instead, the turbine/motor can be located downhole and the activating means exposed to the reactant, to generate the drive medium downhole for driving the rotatable drive member. The downhole tool may in particular comprise or form part of, for example, a setting tool; a cutting tool such as a casing/tubing cutter, a milling tool, a drilling tool, a tubing/casing clean-up or de-scaling and hydrate removal tool; a linear propulsion tool such as a wireline or coiled tubing tractor; and an artificial lift tool.
[0018] Preferably, the rotatable drive member comprises a rotor. The tool may include a tool body defining the reactant chamber. At least part of the isolation means may be moveable relative to a body of the tool to expose the activating means to the reactant. The movable part of the isolation means may comprise a support member and the activating means may be coupled to the support member for moving the activating means into the reactant chamber. The isolation means may further comprise a seal for isolating the activating means from the reactant. The seal may be located in a wall of the reactant chamber and the activating means may be moveable from an isolated position outside the chamber to an exposed position inside the chamber.
[0019] The downhole tool may include a tool connection member through which a force may be exerted on the moveable part of the isolation means, to expose the activating means to the reactant. The connection member may be coupled to the body of the tool and the may be initially restrained from movement with respect to the body until a determined release force is exerted thereon. The connection member may be initially restrained by shearable restraints, such as release screws or pins which may be adapted to shear at the determined release force.
[0020] The downhole tool may further include a fluid medium outlet for directing generated fluid medium to exit the reactant chamber to impinge on and drive the rotatable drive member. The outlet may be closed by the activating means and/or the movable support member when the activating means is isolated from the reactant and may be open when the activating means is exposed to the reactant. Thus a rotary drive force may be generated, and through a suitable coupling with a secondary tool, such as a drill bit, a desired downhole procedure may be carried out. The downhole tool may further include at least one vent for venting spent drive medium from the tool.
[0021] According to a third aspect of the present invention, there is provided a downhole tool for generating a force in a downhole environment, the tool having: a chamber for storing a reactant; activating means for activating the reactant; isolation means for isolating the activating means from the reactant, and for selectively exposing the activating means to the reactant to activate the reactant and generate a drive medium; and a piston member adapted to be driven by the drive medium to generate the force.
[0022] Preferably, the downhole tool is a setting tool or an impact hammer However, the tool may be, for example, a fishing tool; or a cutting tool such as a tubing or casing cutter, wireline sidewall cutter, crimper or the like. The tool may be for generating an axial force and thus the piston member is preferably axially movable. The generated force may be a compressive or tensile force. In use, the downhole tool may advantageously be latched to a secondary tool such as a plug, packer, gauge hanger, anchor or any other similar device, before the activating means is exposed to the reactant. This generates the drive medium, to drive the piston member and exert a setting or jarring force on the secondary tool.
[0023] At least part of the isolation means may be moveable relative to a body of the tool to expose the activating means to the reactant. Preferably, the piston member defines the moveable part of the isolation means, and the activating means may be mounted on or in the piston member. Alternatively, the piston member may be separate from the isolation means. The piston member may be movable in a first direction to at least partly expose the activating means to the reactant. The downhole tool may include a tool connection member coupled to the body of the tool for exerting a force on the tool to relatively move the piston member in the first direction, to initiate the reaction. The piston member may also be moveable in a second direction opposite said first direction under the force of the generated drive medium acting on the piston, to generate the force. The reaction causes rapid movement of the piston relative to the tool body in said second direction, to generate a relatively large compressive or tensile force. The downhole tool may include at least first and second couplings for coupling the tool to a secondary tool, for exerting a force on the secondary tool directed between the respective couplings. The piston member may include or define one of the first and second couplings and the tool body may define the other coupling.
[0024] The isolation means may further include an activation sleeve which may be movable relative to the activating means, for selectively isolating the activating means from the reactant. The activation sleeve may be at least partly restrained against movement with the piston member in said first direction to at least partly expose the activating means to the reactant. The isolation means may also comprise a reactant release sleeve defining a primary barrier to isolate the activating means from the reactant. The release sleeve may be moveable to expose the activating means to the reactant following movement of the piston member in said first direction. The tool may further have a vent for allowing movement of the piston member in said second direction, the vent preventing hydraulic lock-up. The tool may also have a reactant filling port for reactant replenishment. The filling port may include a pressure release valve for allowing venting of spent drive medium from the chamber in the event of the tool experiencing over-pressure during the reaction. Further features of the reactant and the activating means of the second and third aspects are defined above in relation to the first aspect of the present invention.
[0025] According to a fourth aspect of the present invention, there is provided a downhole tool assembly comprising the downhole tool of any one of the first to third aspects of the present invention.
[0026] Further features of the downhole tool are defined above with reference to the first to third aspects of the invention.
[0027] According to a fifth aspect of the present invention, there is provided a method of generating a drive force in a downhole environment, the method comprising the steps of: providing a downhole tool having a reactant and activating means for activating the reactant; isolating the activating means from the reactant to initially prevent the activating means from activating the reactant; locating the tool in a downhole environment; exposing the activating means to the reactant to activate the reactant and generate a drive medium; and directing the generated drive medium to drive a drive member and generate the drive force.
[0028] The downhole tool is preferably charged with reactant at surface and the reactant is isolated from the activating means by sealing the activating means with respect to the reactant. The method may be implemented in a one-shot operation, including the step of removing the downhole tool from the downhole environment after exposure of the activating means to the reactant and optionally recharging the downhole tool with reactant for subsequent further use. Alternatively, the method may further include the step of re-isolating the activating means from the reactant in the downhole environment, to prevent further reaction. Thus the method may further be used in a multi-shot operation which may also include the step of re-exposing the activating means to the reactant, to re-activate the reactant. This may allow further downhole procedures to be carried out before the tool is removed from the downhole environment.
[0029] The activating means may be exposed to the reactant by applying an external force to the downhole tool. The activating means may be coupled to a moveable member of the tool and a force may be exerted on the moveable member to expose the activating means to the reactant. The downhole tool may be suspended from a tool connection member coupled to the moveable member, and a force may be exerted on the tool connection member and thus on the moveable member to move the activating means to expose it to the reactant. The method may further include the step of exerting a determined force on the support member to expose the activating means to the reactant, to overcome a restraining force exerted on the tool connection.
[0030] Alternatively, the method may further include the step of coupling the activating means to the drive member and moving the drive member in a first direction, to expose the activating member to the reactant, to activate the reactant. The generated drive medium may move the drive member in a second, opposite direction to generate the drive force. The drive force may be exerted on a secondary tool coupled to the downhole tool and may be a compressive or tensile load.
BRIEF DESCRIPTION OF THE FIGURES
[0031] Embodiments of the present invention will now be described, by way of example only, with reference to the accompanying drawings, in which:
[0032] FIG. 1 is a schematic illustration of a downhole tool assembly including a downhole tool in accordance with a first embodiment of the present invention, shown in a downhole environment;
[0033] FIGS. 2A and 2B are enlarged, longitudinal sectional and sectioned perspective views, respectively, of the downhole tool of FIG. 1 , shown in a run-in-hole (RIH) position;
[0034] FIGS. 3A and 3B are views similar to FIGS. 2A and 2B , but showing the downhole tool in an in-use position;
[0035] FIG. 4 is a longitudinal sectional view of a downhole tool in accordance with an alternative embodiment of the present invention, and shown in a RIH position;
[0036] FIG. 5 is a view of the downhole tool of FIG. 4 in an activated position; and
[0037] FIG. 6 is a view of the downhole tool of FIG. 4 , in a fully stroked position, following activation as shown in FIG. 5 .
DETAILED DESCRIPTION
[0038] Turning firstly to FIG. 1 , there is shown a schematic illustration of a downhole tool assembly, in the form of a drilling assembly indicated generally by reference numeral 10 . The drilling assembly 10 includes a downhole tool 12 in accordance with a first embodiment of the present invention, which in FIG. 1 is a downhole tool for generating a rotational drive force, in the form of a turbine. The turbine 12 is located in a borehole 14 which has been lined at 16 and cemented at 18 , in a fashion known in the art. The turbine 12 is run into the borehole 14 on coiled tubing 20 , and a drill bit 22 is coupled to and driven by the turbine 12 . The drilling assembly 10 has particular uses in removing obstructions within the lined borehole 14 and in de-scaling/hydrate removal.
[0039] Turning now to FIGS. 2A and 2B , there are shown enlarged longitudinal sectional and sectioned perspective views, respectively, of the turbine 12 of FIG. 1 , shown in a RIH position. The turbine 12 generally comprises a chamber 22 for storing a chemical reactant 23 , activating means in the form of catalyst means 24 for activating the reactant, isolation means indicated generally by reference numeral 26 and a drive member 28 . The isolation means initially isolates the catalyst means 24 from the reactant 23 , but also allows the catalyst means 24 to be selectively exposed to the reactant 23 . This activates the reactant 23 , generating a drive medium for driving the drive member 28 , to in-turn generate a drive force.
[0040] In more detail, the turbine 12 has an outer body 30 which defines the chamber 22 . The isolation means includes a floating piston 32 , a fixed seal 34 and a movable member in the form of a support rod 36 . The body 30 has a male pin end 38 , by which the turbine 12 is coupled to the coiled tubing 20 , and a tool connection member 40 extends through the end 38 and is secured to the support rod 36 . The tool connection member 40 is initially restrained from movement by shearable release screws 42 which secure it to the outer body 30 .
[0041] At a lower end of the tool (to the right in FIGS. 2A and 2B ), the drive member 28 , which takes the form of a turbine rotor, is mounted in a rotor housing 44 . A lip 46 of the seal 34 is held between the body 30 and rotor housing 44 , to hold the seal 34 in place. The rotor 28 has a lower male pin end 48 for coupling to the drill bit 21 . A number of vent ports 50 are spaced around a circumference of the rotor housing 44 (two shown in FIGS. 2 A/ 2 B), and these allow venting of spent drive medium from the turbine 12 .
[0042] The reactant 23 in the chamber 22 is an oxidising agent, in particular hydrogen peroxide (H 2 O 2 ), whilst the catalyst means 24 typically takes the form of an iron or copper catalyst, such as iron or copper sulphate. In the RIH position of FIGS. 2 A/ 2 B, the catalyst 24 is isolated from the reactant 23 by the fixed seal 34 , through which the support rod 36 protrudes, and an O-ring 52 seals the outer surface of the rod 36 . The turbine 12 is maintained in this configuration until the drilling assembly 10 has been run into the borehole 14 to the desired location, where it is required to carry out a drilling operation.
[0043] To activate the turbine 12 , the tool connection 40 is engaged and pulled to shear the release screws 42 , as shown in FIGS. 3A and 3B . This draws the catalyst 24 into the chamber 22 , where it is exposed to the H 2 O 2 reactant 23 . A collar 54 on the support rod 36 abuts an end face 56 of the chamber 22 , to restrain the rod 36 against further movement. As the support rod 36 moves, the floating seal 32 is carried with it, urged against the collar 54 by the pressure of the generated drive medium. Hydraulic lock of the floating piston 32 is prevented by the provision of bleed ports 58 in the outer body 30 , which allow bleed of fluid from the region 60 of the chamber 22 to annulus.
[0044] When the catalyst 24 is exposed to the H 2 O 2 , an exothermic reaction takes place and the H 2 O 2 decomposes into oxygen and steam, constituting the drive medium. The generated drive medium is directed through an outlet passage 62 in the fixed seal 34 , which has been opened by movement of the rod 36 , and is thus jetted onto the rotor blades 64 of the rotor 28 , which is rotated to in-turn drive the drill bit 21 . Spent drive fluid discharges through the vent ports 50 to annulus, as indicated by the arrows A in FIG. 3A . When the supply of H 2 O 2 has been used, the reaction ceases such that no further drive fluid is generated and the rotor 28 stops rotating. Accordingly, the chamber 22 is sized to contain sufficient H 2 O 2 to carry out the desired drilling operation, as specified above. The downhole tool assembly 10 is then pulled out of hole (POOH) for replenishment of the H 2 O 2 reactant 23 .
[0045] Turning now to FIGS. 4-6 , FIG. 4 shows a longitudinal sectional view of a downhole tool in accordance with an alternative embodiment of the present invention, shown in a RIH position, the tool indicated generally by reference numeral 112 . The tool 112 is suitable for generating a force in a downhole environment, in particular an axial force. Like components of the tool 112 with the tool 12 of FIGS. 2A-3B share the same reference numerals, incremented by 100 . The setting tool 112 is run on a string of coiled tubing or wireline, in a similar fashion to the turbine 12 . The tool 112 takes the form of a setting tool for exerting a setting force on a secondary tool, such as a plug or packer, or for locking gauge hanger anchors or any other downhole tool requiring a relatively high compressive or tensile load to set. The setting tool 112 includes a chamber 122 for storing H 2 O 2 reactant 123 and a catalyst 124 . Isolation means 126 isolates the catalyst 124 from the H 2 O 2 123 , in a similar fashion to the turbine 12 . A piston member 66 is driven by drive medium generated when the catalyst 124 is exposed to the reactant 123 , to generate an axially directed force.
[0046] In more detail, the setting tool 112 has an outer body 130 and a tool connection 140 coupled to the body 130 by a threaded joint 68 . The piston member 66 is movably mounted in the casing 130 and defines a moveable member of the isolation means 126 . A lower end (right side in FIG. 4 ) of the body 130 carries a male threaded coupling 70 for connecting the setting tool 112 to a secondary tool to be set. Similarly, the piston member 66 includes a coupling 72 for coupling the piston 66 to the secondary tool at a second location. As will be described below, this allows a force to be exerted between the two couplings 70 and 72 , to exert a tensile (or compressive) setting force upon the secondary tool.
[0047] An upper end (left hand side in FIG. 4 ) of the piston 66 carries a sliding O-ring seal 74 and the body 130 includes a number of circumferentially spaced bleed ports 158 , to prevent hydraulic lock of the piston 66 . The catalyst 124 comprise a ring located in a groove 76 in the piston 66 . O-ring seals 78 and 80 straddle the catalyst 124 , sealing against an activation sleeve 82 of the isolation means 126 . The isolation means 126 also includes a reactant release sleeve 84 which, in the RIH position of FIG. 4 , acts as a primary barrier to isolate the catalyst 124 from the reactant 123 , by sealing against a shoulder 86 in the body 130 through an O-ring seal 88 . The body 130 also includes a reactant filling port 90 in which a pressure relief valve 92 is mounted. This both allows the reactant 123 to be replenished when the tool is POOH after the downhole procedure has been completed, and allows bleed of reactant 123 and/or generated drive medium in the event of over-pressure during the reaction. The setting tool 112 is secured through the couplings 70 and 72 to the secondary tool to be set.
[0048] The reaction is initiated by exerting a pull on the body 130 , as shown in FIG. 5 . This causes a movement of the piston 66 relative to the casing 130 in a first direction indicated by the arrow B. During this movement, the activation sleeve 82 is restrained against movement with the piston 66 by the shoulder 86 , and this uncovers the catalyst 124 . In addition, the reactant release sleeve 84 is carried out of sealing engagement with the shoulder 86 by a shoulder 87 of the piston 66 , and the catalyst 124 is then fully exposed to the reactant 123 , to initiate the reaction.
[0049] As shown in the fully activated position of FIG. 6 , this causes the piston 66 to move rapidly upwardly in the direction of the arrow C, under the forcing action of the generated drive medium. During this movement, the piston 66 expels fluid from the region 160 in the body 130 through the bleed ports 158 . Thus, a high tensile setting force is exerted on the secondary tool as the distance between the first and second couplings 70 and 72 is rapidly shortened. This sets the secondary tool and the setting tool 112 is then disconnected and POOH. The H 2 O 2 reactant 123 may then be replenished through the filling port 90 for subsequent further use of the setting tool.
[0050] Various modifications may be made to the foregoing within the scope of the present invention. For example, the tool 12 has uses in other downhole tool assemblies, such as cutting tools. These cutting tools include milling tools and tubing cutters, where centrifugal blades are fitted to the turbine 12 and are rotated to expand outwards to effect a circular cutting motion, used to cut or profile a wellbore tubular. The turbine 12 may also be used as a setting tool, for setting secondary downhole tools, as an artificial lift tool, or as a linear propulsion tool, fitted to a tractor device for propelling tools, gauges and the like along deviated or horizontal sections of wellbore.
[0051] The tool 112 may be used to retrieve tools lodged in a borehole by exerting a high pulling or impact force on the tool. Also, attachments may be provided such as tubing cutters, wireline sidewall cutters, crimpers or the like activated by the axial force generated by the tool.
[0052] The downhole tools may thus be used for displacing tools lodged in boreholes, or for the removal of sedimentary deposits or any other obstruction, through associated cutting/impact assemblies. | An apparatus and method for generating a drive force in a downhole environment includes chambers of a reactant and a catalyst, respectively, that are maintained separate until selectively exposed to one another. Once exposed, the reactant and catalyst produce expanding fluid pressure and sometimes heat. The products of the reaction are directed to a drive member to carry out a desired operation in the downhole environment. | 4 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims priority from U.S. Provisional Application Serial No. 60/218,211 filed Jul. 14, 2000 entitled MULTIPLE USE TRAILER and from U.S. application Ser. No. 09/902,191 filed Jul. 10, 2001 and entitled MULTI-PURPOSE TRAILER, each of which is incorporated herein by reference.
FIELD OF THE INVENTION
[0002] This invention relates generally to the field of utility trailers, and more particularly to a utility trailer system with an easily removable bed.
BACKGROUND OF THE INVENTION
[0003] A trailer, towed behind a vehicle, is a common item used to transport recreational vehicles, such as snowmobiles, boats, jet skis, motorcycles, and the like. These vehicles are too big to fit into today's smaller cars, but they are not too heavy to tow with the small car as long as the trailer is lightweight. Many people are forced into either purchasing several complete trailers specialized to carry a particular recreational vehicle, or purchasing a large sport-utility vehicle or truck to pull a heavy trailer that may haul a variety of objects. Either of these possibilities places an increased demand on storage space and fuel usage. A consumer may save a significant amount of space and fuel by eliminating the need for a large vehicle, and eliminating the need for multiple sets of axles, wheels, and trailer tongues. Consequently, a lightweight multipurpose trailer having a changeable cargo deck is needed to transport and store the hobby vehicles without adding unnecessary parts and weight.
[0004] The prior art teaches several types of trailer systems having changeable cargo containers or decks. Most systems consist of a trailer that is functional in itself for hauling some type of cargo without any type of added structure. Others have a heavy structural main frame that has a correspondingly cumbersome system of moving the heavy cargo containers on an off the main frame. These systems work well for their intended purpose of hauling heavy cargo such as cars, horses, or heavy equipment, but they are inefficient for the transport of light cargo.
SUMMARY OF THE INVENTION
[0005] Briefly stated, a lightweight multipurpose trailer particularly designed to separate into two parts, a base chassis and cargo support deck. The base chassis provides the hitch beam, axles, suspension, and wheels, but the chassis does not have the necessary structure or strength to carry a load without the addition of the cargo support deck. The attached cargo support deck provides the required strength and rigidity through its connections directly to the axle and the hitch beam. Different customized cargo support decks each fit on the base chassis, but can be stored separately with or without their cargo.
[0006] According to an embodiment of the invention, a multipurpose trailer system includes a chassis, the chassis including at least one axle and only one main beam, the axle including first and second ends; a first suspension attached to the first end of the axle, and a second suspension attached to the second end of the axle; a first wheel attached to the first suspension, and a second wheel attached to the second suspension; the axle having first, second and third axle portions, the first axle portion extending from the first end of the axle to the third axle portion, the second axle portion extending from the second end of the axle to the third axle portion; the main beam attached to a center of the axle on the third axle portion; and a cargo deck including at least first, second, and third connectors for removably mounting the cargo deck to the chassis, the first and second connectors mounted on the axle and/or the cargo deck, the third connector mounted on the beam and/or the cargo deck; wherein the cargo deck provides structural rigidity to the chassis through the first, second and third connectors, the structural rigidity being required to transport a load or a cargo from a first location to a second location.
[0007] According to an embodiment of the invention, a multipurpose trailer system includes deck means for locating and positioning cargo; moving means for transporting the deck means from a first location to a second location when the moving means is connected to a prime mover; and attachment means for removably attaching the deck means to the moving means; wherein the securing means being attached to the moving means by the attachment means provides lateral strength required by the moving means to carry the cargo from the first location to the second location without the chassis bending or failing.
[0008] According to an embodiment of the invention, a method of making a multipurpose trailer system includes the steps of (a) providing an axle with a first and second ends and first, second and third portions, the first portion extending from the first end of the axle to the third axle portion, and the second axle portion extending from the second end of the axle to the third portion; (b) connecting a main beam to the third portion a center of the axle, wherein the main beam and the axle in combination are not sufficiently rigid to transport cargo from a first location to a second location; (d) connecting a first suspension to the first portion of the axle, and connecting a second suspension to the second portion of the axle; (e) connecting a first wheel to the first suspension, and connecting a second wheel to the second suspension; (f) providing a cargo deck with a front side and a back side;, the front side positioned near the main beam, the back side located opposite the front side, the cargo deck with sufficient rigidity to transport cargo from the first location to the second location; (g) removably attaching the cargo deck to the first and second portions of the axle; and (h) removably attaching the front side of the cargo deck to the main beam, wherein steps (g) and (h) impart to the cargo deck sufficient rigidity wherein cargo is transportable via the trailer system from a first location to a second location.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] [0009]FIG. 1 shows a perspective view of a first embodiment of the chassis of the present invention.
[0010] [0010]FIG. 2 shows a perspective view of a second embodiment of the chassis of the present invention.
[0011] [0011]FIG. 3 shows a perspective view of a cargo support deck positioned in spaced relation to the chassis of FIG. 2.
[0012] [0012]FIG. 4 shows a fragmentary perspective view of the mounting structure of the chassis and cargo deck of the present invention.
[0013] [0013]FIG. 5 shows a perspective view of the cargo support deck support/storage device.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0014] Referring to FIG. 1, a base chassis 10 generally includes an axle 12 having a conventional suspension systems 14 , 16 , such as leaf springs (not shown) or a torsion beam and lever arm system (shown), attached to its opposing ends, wheels 18 , 20 rotatably attached to suspension systems 14 , 16 , respectively, a main beam 22 attached to and extending forwardly from the center of axle 12 at connection 38 , a towing hitch 24 attached to the forward end of beam 22 , a pair of brackets 26 , 28 attached to axle 12 adjacent each suspension system 14 , 16 , respectively, two pairs of dowel pins 30 , 32 attached to brackets 26 , 28 , respectively, a pair of holes 34 , 36 through brackets 26 , 28 , respectively, and a mounting bracket 40 attached to beam 22 at an intermediate position therealong, with a hole 42 formed through bracket 40 . Axle 12 , connection 38 and beam 22 are sized primarily to withstand the torsional stress generated by suspension systems 14 , 16 with the weight of axle 12 , connection 40 , and beam 22 . Additional torsional loads generated by suspension systems 14 , 16 when a cargo deck is attached are cancelled by brackets 26 , 28 . Connection 40 is sized to withstand the force required to turn chassis 10 without any additional cargo. Beam 22 is sized to withstand the axial force required to pull both chassis 10 and any cargo deck attached. Any loads in addition to those created by the weight of chassis 10 when no cargo deck is attached may cause axle 12 , connection 40 , and/or beam 22 to bend or fail.
[0015] Referring to FIG. 2, an alternate embodiment of the base chassis of the present invention is illustrated. Chassis 100 generally includes a pair of axles 102 , 104 that telescopically engage the opposing ends of an inner axle member 106 , and which include a pair of wheels 108 , 110 rotatably connected thereto with a traditional suspension, and a beam assembly, designated generally by reference numeral 112 . Beam assembly 112 includes a tubular member 114 attached to and extending forwardly from inner axle member 106 , and a beam member 116 telescopically engaged with and extending forwardly from tubular member 114 . Beam member 116 includes a towing hitch 118 attached to its forward end, and a mounting bracket 120 attached an intermediate position therealong. A conventional fastener 122 , such as a pin, interconnects tubular member 114 and beam member 116 .
[0016] Base chassis 100 further includes a pair of mounting brackets 124 , 126 attached to axles 102 , 104 , respectively, and a width adjustment assembly, designated generally by reference numeral 128 , of which inner axle member 106 forms a part thereof. Width adjustment assembly 128 further includes a plate 130 mounted to the upper surface of tubular member 114 for rotation about its central, vertical axis Y-Y, an arm 132 extending outwardly from plate 130 , and a pair of mechanical linkages 134 , 136 extending between and interconnecting plate 130 (linkages 134 , 136 are connected to diagonally opposite corners of plate 130 ) to mounting brackets 124 , 126 , respectively. A user may grasp arm 132 and rotate it either clockwise or counter-clockwise, thereby causing linkages 134 , 136 to either decrease or increase the effective width W of base chassis 100 .
[0017] Referring to FIG. 3, a cargo deck 200 may be interconnected to chassis 10 or 100 . It should be noted that FIG. 3 illustrates deck 200 being connected to chassis 100 , but it could also be attached to chassis 10 in the same manner. Deck 200 includes a bottom surface 202 , a pair of joists 204 , 206 attached to bottom surface 202 and extending parallel to the longitudinal axis of deck 200 adjacent opposing sides thereof, and a centrally extending joist 208 attached to bottom surface 202 . Mounting tabs 210 , 212 are attached to joists 204 , 206 , respectively, while hole 218 is formed through the forward end of joist 208 . To interconnect deck 200 to chassis 100 (or chassis 10 ), a user positions mounting tabs 210 , 212 in engaging relation to mounting brackets 124 , 126 (or mounting brackets 26 , 28 ), respectively, and joist 208 in engaging relation to mounting bracket (or mounting bracket 40 ). Mounting hole 218 formed through joist 208 and mounting hole 120 formed through bracket 140 should be axially aligned such that conventional fasteners, such as pins, may be used to securely connect deck 200 to beam 116 (or beam 22 ).
[0018] Referring to FIG. 4, holes 216 , 34 formed through mounting tab 210 (and 212 ) and mounting bracket 26 (and 28 ), respectively, should be axially aligned, while dowel pins 30 axially engage with holes 220 formed in joist 204 , so that conventional fasteners, such as pins, may be used to securely interconnect deck 200 to axle 12 (or axles 102 . 104 ).
[0019] Referring to FIG. 5, a cargo deck support, designated generally by reference numeral 300 , is shown with a pair of supports 300 needed to support a cargo deck. Support 300 generally includes a U-shaped body having a medial portion 302 and a pair of legs 304 , 306 extending in parallel relation to one another and outward perpendicular from opposing ends of medial portion 302 . Leg 304 includes an arm 308 extending outward perpendicular from its free terminal end, and leg 306 includes a series of longitudinally spaced, axially aligned pairs of holes 310 formed therethrough adjacent its free terminal end. An arm 312 is movably and securely interconnected to leg 306 via pin 314 , extending in perpendicular relation to arm 306 and in parallel relation to arm 308 .
[0020] Support 300 is used to hold cargo deck 200 (typically with cargo positioned thereon) in a stored location while giving the owner use of chassis 10 (or 100 , for convenience only chassis 10 is referred to hereafter) to move other cargo decks. To store a cargo deck 200 , the user moves chassis 10 with deck 200 thereon to the desired storage location. A conventional jack, or other hoisting device, is then be attached to or positioned under the forward end of chassis 10 . The jack is lowered to a predetermined distance off the ground. The user then disconnects deck 200 from mounts 26 , 28 on chassis 10 . The user then positions a support 300 under each of the side edges of chassis 10 with medial portion 302 engaging the ground and legs 304 , 306 extending vertically upwardly therefrom. This step and the following steps are done to each of the two supports 300 . The user then uses the jack or hoisting device to raise the front of chassis 10 to a predetermined distance off the ground. Arm 312 is then vertically adjusted, if necessary, to engage bottom surface 202 of deck 200 , after which the user disconnects beam 22 from deck 200 and lowers chassis 10 from deck 200 , thereby leaving deck 200 resting on supports 300 . Chassis 10 may then be moved either forward or rearward from beneath deck 200 , and then used to carry another deck 200 , typically with a different cargo, such as a snowmobile instead of an ATV.
[0021] While the present invention has been described with reference to a particular preferred embodiment and the accompanying drawings, it will be understood by those skilled in the art that the invention is not limited to the preferred embodiment and that various modifications and the like could be made thereto without departing from the scope of the invention as defined in the following claims. | A lightweight multipurpose trailer which separates into two parts includes a base chassis and cargo deck. The base chassis provides the hitch beam, axles, suspension, and wheels, but the chassis alone does not have the necessary structure or strength to carry a load without the addition of the cargo deck. The attached cargo deck provides the required strength and rigidity through its connections directly to the axle and the hitch beam. Different customized cargo support decks each fit on the base chassis, but can be stored separately with or without their cargo. | 1 |
BACKGROUND OF THE INVENTION
The invention relates to a new method for concentrating and dehydrating sewage sludge including activated sludge of an aerated biologic clearing step.
The aim to be achieved by the methods in industrial and/or local bio-aerobic sewage clarification is the production of an easily filtrable, compact sewage sludge having a high amount of dry substance contents in the filter cake. The reduction of the volume of sludge accompanying a high amount of dry substance contents by separating off the water portion permits a cost-effective and energy-saving further treatment of the sewage sludge by storing it on dumping grounds, burning it or using it in agriculture.
Sewage sludge consists of the so-called primary sludge obtained in the preliminary sedimentation by precipitation in presence of organic and/or inorganic flocculators and of the activated sludge produced in the biologic clearing step. Depending on the type and operating mode of the sewage treatment plant the sewage sludge contains between about 10 % to 90 % by weight of activated sludge. While the primary sludge corresponding to its origin by precipitation in the preliminary sedimentation basin generally shows good filterability properties (dry substance contents and filtration velocity), mixtures out of primary sludge and activated sludge as a rule are difficult to concentrate and dehydrate.
According to the state of art a so-called flocculation aid is added to the activated sludge, the so-called excess sludge, originating from the biologic clarifications step in the secondary sedimentation basin for improving the sedimentation and dehydration behaviour. The thus pretreated excess sludge is mixed with the primary sludge in the secondary concentrator and the sludge mixture is dehydrated in centrifuges, band filter presses or chamber filter presses.
The adding of flocculation aids can also be effected in another step, e.g. in the so-called secondary concentration--dosed into the mixture of primary and excess sludge--instead of being effected in the secondary sedimentation basin. The filter or centrifuge cake of the sewage sludge always contains more or less large portions of organic and/or inorganic flocculation aids apart from primary and activated sludge. The composition and the way of use of flocculation aids is known to the expert. In a largely used method the sludge to be filtered is treated with iron(III)salt, e.g. iron(III)-chloride and calcium hydroxide, in such manner that about 20 to 60 kgs of iron(III)chloride and 75 to 180 kgs of calcium hydroxide per ton of dry solid substance are used. By this way of action a compact, easily filterable sewage sludge is obained which, however, is loaded with additional amounts of slag-forming inorganic substances.
According to this so-called iron-lime method preferably organic polymeric flocculators are used for concentration/dehydration of sewage sludge including activated sludge. Polymeric flocculators are water-soluble, chain-forming polymerizates mostly produced by polymerization of acrylamide (e.g. as defined in the German publication 2,025,725 or 2,337,337 or Japan Kokai 75/161,479 or Japan Kokai 75/53,274 or Japan Kokai No. 74/59,855). It is, however, also possible to condense other polymerizable monomers, e.g. ethylene oxide (USSR Patent No. 1,204,576), ethyleneimine, allyl guanidines (U.S. Pat. No. 3,878,170) or quarternary carboxylic acid esters (Japan Kokai No. 76/04,084) or polyamines (U.S. Pat. No. 3,174,928, Spanish Patent No. 287,939, Japan Kokai Tokio Koho No. 86/192,734) to polyelectrolytes in chain form. In dependance on their electrostatic charge in aqueous solution a distinction is made between nonionnic, anion-active and cation-active polymeric flocculators. The combination, too, of inorganic/organic agents, such as pulverized brown coal plus polymers, is known for use as flocculator to the expert.
Per ton of solid substance about 1 kilogram to 7 kilograms of polymeric polyelectrolyte are required for achieving a sufficiently fast concentration and dehydration of the sewage sludge. By the use of organic polyelectrolytes the problem of the large amount of slag-forming inorganic substances in the filter cake of the sewage sludge (iron-lime method) is solved, however, the organic flocculators used instead represent a substantial cost factor which can decisively reduce the economy of sludge concentration and dehydration.
Therefore, numerous attempts have been made to modify the operation mode of sludge concentration and dehydration by means of the above-named organic polymeric flocculators in such manner that the required amount used is reduced to a minimum.
Japanese patent specification Kokai Tokio Koho No. 79/113,954, e.g., teaches the use of cation-active non-ionic copolymers of definite molar conditions for increasing the efficiency in the dehydration of sludges. European patent application 159,178 as well as Japan Kokai Tokio Koho No. 87/102,892 teach the use of synergistically acting inorganic/organic flocculating/charging agents for the purpose of saving polymers. In the patent specification Japan Kokai No. 75/141,850 a method is described for concentrating/dehydrating sewage sludges with reduced polymer consumption, in which method the sludge primarily is treated with a part of the sedimented clarifying agent of a previous precipitation, whereupon concentration of the pretreated sludge is effected using a reduced amount of fresh polymer. Japan Kokai No. 75/86,476 describes a synergetically acting combination of aluminium salts and non-ionic polyacrylamide for sludge dehydration.
The above-described synergetic methods require an accurate survey of the properties of the sludge to be dehydrated as well as a continuous checking of the precipitation/dehydration process for being able to make use of the advantages cited in the patent specifications. Japan Kokai Koho No. 87/132,600 describes, e.g., the analytic expenditure for predicting the dehydration behaviour of the sewage sludge. With the large variations of the flocculation and dehydration behaviour of mixed sludge ocurring in local and industrial sewage sludge treatment the use of the above-mentioned synergetic methods is limited.
It is, therefore, the object of the present invention to find a method for concentrating/dehydrating sewage sludge, which method permits a real reduction of the required amount of organic and/or inorganic flocculation agents independently from variations in the flocculation and dehydration behaviour of sewage sludge comprising activated sludge.
It has been found that said problem can be solved in accordance with the present invention in that the activated sludge portion of the sewage sludge to be dehydrated is produced in an aerated biologic clarification step in the presence of at least one compound selected from the group consisting of folic acid, dihydrofolic acid and at least one salt thereof.
SUMMARY OF THE INVENTION
The present invention relates to a method for concentrating/ dehydrating sewage sludge including activated sludge in presence of organic polyelectrolytes and/or inorganic flocculators, which comprises producting the activated sludge portion in an aerated biologic clarification step in presence of at least one compound selected from the group consisting of folic acid, dihydrofolic acid and at least one salt thereof.
DETAILED DESCRIPTION OF THE INVENTION
The procedural method according to the present invention independently from variations in the composition and the dehydration behaviour of the primary sludge permits a simultaneous operation of the sludge concentration and filtration/ centrifugation and requires only minimal efforts for analytically surveying the procedural steps. Furthermore, the procedural method according to the present invention permits, contrary to hitherto known methods, to effect a significant reduction of flocculators without new substances detrimental for the environment being introduced into the circulation of industrial or local sewage water purification.
The folic acid and/or dihydrofolic acid and/or the salts thereof are added in amounts of 5 to 1.1 ppm, preferably 1 to 0.01 ppm, based on the sewage water flowing into the biologic clarification step.
According to a preferred embodiment of the present invention continuously about 1 to 0.01 ppm of folic acid and/or dihydrofolic acid and/or at least one ammonium alkali metal salt, alkaline earth metal salt and/or alkanolammonium salt thereof are dosingly added to the prepurified sewage water flowing into the biologic clarification step.
In another preferred embodiment of the procedural method according to the present invention continuously 1 to 0.01 ppm, based on the prepurified sewage water flowing into the clarification step, of folic acid and/or dihydrofolic acid and/or at least one ammonium alkali metal salt, alkaline earth-metal salt and/or alkanolammonium salt thereof is dosingly added into the so-called sludge back flow. After some days the amount of flocculators priorily having been required in the sewage sludge concentration/dehydration can be reduced step by step without worsening of the sedimentation and dehydration behaviour of the sewage sludge.
If the inventive method is carried out by dosingly adding aqueous alkali or alkaline earth metal salt solutions or alkanolammonium salts of folic acid ##STR1## to the activated sludge in the aerobic biologic clarification step and in dehydrating the thus treated excess sludge alone or mixed with primary sludge, due to the insufficient stability of the folic acid in aqueous solution a concentration of about 0.5 to 3 ppm of folic acid with respect to the sewage water flowing into the activated basin is required for achieving the desired improvement effect in dehydration of the sewage sludge.
If in contrast thereto, as can be seen from the Belgian patent specification No. 88.00333, instead of pure folic acid its derivative dihydrofolic acid ##STR2## and/or mixtures of folic acid and dihydrofolic acid are dosingly added to the activated sludge in form of the alkali or alkaline earth metal salt solutions or alkanolammonium salt solutions, so due to the good stability of the folic acid/dihydrofolic acid solution in aqueous solution only concentrations of about 0.01 to 0.1 ppm of folic acid/dihydrofolic acid mixture, based on the sewage water flowing into the activated basin, are required for achieving the desired improvement effect in dehydrating the sewage sludge.
Stable folic acid preparations are described in EP-87 118 082.4. The term "alkali metal salts" used herein in intended to mean the lithium, sodiumm, potassium, rubidium and caesium salts.
The term "alkaline earth metal salts" used herein is intended to mean the magnesium, calcium, strontium and barium salts.
Under the above-mentioned expression "ammonium salts" ammonium salts as well as also tetraalkylammonium salts, with the cation NH 4 + or NR 4 + , respectively, are to be understood, wherein R is an alkyl residue with preferably 1 to 6, in particular 1 to 4, especially 1 to 3 carbon atoms.
The ammonium salt preferably is a salt of the above-named organic acids with a dialkanolamine of the formula ##STR3## wherein, R1 is hydrogen and/or hydroxyethyl and/or hydroxypropyl.
One feature of the method according to the present invention lies in the fact that the effect of improved sludge dehydration will occur with a temporal delay only. Generally 5 to 10 days of first runnings upon adding of folic acid/dihydrofolic acid solution are required before the effect will take place. If the adding process is interrupted, the effect may still be observed for several days.
In spite of the fact that it is known that folic acid hardly is present in sewage treatment plants and stimulates the growth of various microorganisms (H. Mohr; Folic Acid - Micronutrient and Growthpromotor for Bakteria and Fungi. An Outline, BioTechnologie 10, 1987) it could not have been expected that such an synergistic effect would occur with usual flocculators upon addition of the above-mentioned folic acid and/or dihydrofolic acid and/or the salts thereof to the biologic aerobe clarification step in the dehydration of mixed sludge.
The procedural method according to the present invention will be explained in more detail using the following examples without being restricted thereto.
DETAILED ACCOUNT OF EXAMPLES OF THE INVENTION
EXAMPLE 1
In a local sewage treatment plant a mixture of 30 to 40 % by weight of activated sludge and 70 to 60 % by weight of primary sludge were treated in a chamber filter press plant. In order to increase its fiterability, the mixed sludge being in the detention container before the filter press contained about 4 % by weight of iron(III)chloride and 8 % by weight of calcium hydroxide, based on the sludge dry substance. With this amount of flocculators a filter output between 26 and 40 kilograms/m 2 /bar/hour was achieved. The contents of dry substance sewage sludge in the filter cake was about 26/28 % by weight. This procedural method and the operating parameters have proved to be constant and optimal during a period of time of 6 months prior to a change to the procedural method of the present invention.
For the purpose of changing to the procedural method according to the present invention a 0.5-% solution of the disodium salt of the folic acid in distilled water was dosingly added into the inlet to the activated basin by means of a dropping means. Every day about 2500 cbm of sewage water from the preliminary sedimentation flew through the activated basin. The sludge concentration in the activated basin was from 2 to 4 grams of dry substance per liter, and the chemical oxygen demand in the preliminary sedimentation basin was from 700 to 1100 mg per liter. These operating values corresponded to those of the prior period. The dosing means for the aqueous folic acid solution was set such that 1.1 grams of sodium folat were dosingly added to each cubic meter of presedimented sewage water flowing into the activated basin (= folic acid concentration or 1 ppm).
Ten days after the beginning of the folat addition the filter output had increased to 50 to 60 kilograms/m 2 /bar/hour. The iron/lime amount thereupon was reduced to about 3 % by weight of iron(III)chloride and 4 % by weight of calcium hydroxide based on the sludge dry substance, no decrease of the filter output taking place. Upon ten further days of folat dosing the iron/lime amount could be reduced to about 2 % by weight of iron(III)chloride and 3 % by weight of calcium hydroxide, based on the sludge dry substance, the filter output remaining constant at 50 to 60 kilograms/m 2 /bar /hour.
After 40 days the folat dosing was interrupted, thereafter the good filter output being maintained up to the 48th day and then decreasing visibly. After 60 days again an amount of flocculator of about 4 % by weight of iron(III)chloride and 8 % by weight of calcium hydroxide, based on the sludge dry substance, was required for achieving a sufficient filter output.
EXAMPLE 2 (COMPARATIVE EXAMPLE)
The test of example 1 was repeated in the same sewage treatment plant, in dosingly adding 0.11 grams of sodium folat dissolved in one liter of water to each cubic meter of presedimented sewage water flowing into the activated basin. (= folic acid concentration of 0.1 ppm). An improved filter output and thus a reduction of the iron/lime amount was not achieved.
EXAMPLE 3
In a mineral oil refining plant a load per day with a biological oxygen demand of 2000 kg BOD5/d (BOD5=biological oxygen demand in 5 days) was degraded by means of four activated basins in serial connection. The activated sludge arrived in a secondary sedimentation basin where the excess sludge was drained off and conveyed to a sludge detention basin. The excess sludge was dehydrated in three structurally identical chamber filter presses with the aid of 20 kilograms of lime hydrate and 8 kilograms of iron(III)chloride per cubic meter of filter cake from the filter press for obtaining a disposable filter cake with about 35 % of solid substance contents.
For the purpose of changing to the procedural method according to the present invention 0.23 grams of technical grade 90 % calcium dihydrofolate dihydrate--predissolved in 1 kilogram of distilled water--was dosingly added to each cubic meter of sewage water flowing into the second of the activated basins arranged in series (folic acid concentration of 0.018 ppm, dihydrofolic acid concentration =0.18 ppm). After 30 days of operation on basis of the procedural method according to the present invention the filtration speed for the sewage sludge (activated sludge portion 70 % by weight) had increased such that at a solid substance concentration remaining constant instead of three only two of the present chamber filter presses were still required for dehydrating the incoming sludge load. Simultaneously the demand of flocculators could be reduced to 10 kilograms of lime hydrate and 4 kilograms of iron(III)chloride per cubic meter of filter cake.
EXAMPLE 4
In accordance with the Belgian patent specification 88.00333, example 12, an aqueous solution of folic acid, dihydrofolic acid and citric acid was produced using sodium hydroxide solution and potassium hydroxide solution. The pH value of the solution was 10.4. 100 grams of the solution contained 8 mmol of folic acid salt, 8 mmol of dihydrofolic acid salt and 5 mmol of citric acid salt.
The above folic acid/dihydrofolic acid preparation was - upon having been further diluted with tap water in a ratio of 1:100 parts by volume--dosingly added into the activated sludge back flow line of the aerated clarification step of a local sewage water administration union. The sewage treatment plant did not include a digestion tower, and the dehydration of the sewage sludge was effected with the aid of a high-molecular, water soluble, cationic polymer on basis of acrylic acid esters. Every day 60,000 cubic meters of sewage water were introduced from the presedimentation basin into the four parallel activated sludge basins equipped with dip tube aeration. It was taken account of the fact that a part of the dosingly added folic acid/dihydrofolic acid preparation was lost, because only 70 % of the back-flow sludge was transported back into the activated basins. Thus an effective dosis concentration of 0.01 ppm of folic acid and 0.01 ppm of dihydrofolic acid in the sewage water flowing into each of the parallel activated basins was the result.
After 15 days of operation with the procedural method according to the present invention--maintaining the continuous amount of folate dosing--the amount of cationic polymer used in dehydration of the sewage sludge could be reduced to 30 % of the value required prior to the use of the folic acid/dihydrofolic acid preparation. | In the method for concentrating/dehydrating sewage sludge including activated sludge with the aid of organic polyelectrolytes and/or inorganic flocculators the activated sludge portion is produced in an aerated biologic clearing step in presence of--based on the amount of liquid flowing into the clearing step--5 to 0.01 parts by weight per million parts by weight of at least one compound selected from the group consisting of folic acid, dihydrofolic acid and at least an ammonium alkali metal salt, alkaline earth metal salt and alkanolammonium salt thereof. | 2 |
BACKGROUND OF PRIOR ART
Flow washers are conventionally utilized in water discharging conduits in an effort to control the flow of water therethrough so as to make the flow volume more uniform under various or varying source pressure conditions. Such flow washers are frequently utilized under such varying conditions in combination with timers, in an effort to dispense a predetermined quantity of water where such is desired, as in washing machines. Since city water pressures vary between 15 p.s.i. and 120 p.s.i., the flow volume through a given valve will vary widely, absent such a flow washer.
Flow washers presently in common use are generally discs constructed of a flexible resilient material and having a central orifice extending therethrough, the washer distorting to different extents under different pressure conditions and thereby reducing the size of its orifice as the source pressure is elevated. As a consequence, some measure of control is accomplished at the higher pressures, but at the lower ranges of pressure, such flow washers are inadequate in that they do not readily provide for an adequate flow therethrough. Thus, for such flow washers, at lower source pressures ranges, the volume of flow is substantially less than that which will be permitted to pass at more elevated source pressures and therefor, it is impossible to properly time such a machine so as to insure that the desired amount of flow will result at both low and elevated source pressures. My invention is directed to solving this problem in a simple and relatively inexpensive manner.
BRIEF SUMMARY OF THE INVENTION
My invention provides an essentially uniform flow over a wider and important range of source pressures. As a consequence, my flow washer, when used in combination with a timer, will provide essentially a uniform volume of flow over the entire normal range of source pressures. I accomplish this by constructing the flow washer differently so as to inherently increase, as a result of its structure, the amount of water which is permitted to pass, therethrough throughout the lower ranges of source pressure. In other words, I have provided a flow washer with different structural characteristics which causes a greater flow to pass therethrough at lower pressures.
I do this by defining the orifice of the flow washer with a plurality of closely adjacent but spaced radially and axially extending fins which are supported by an annular outer wall. At lower pressures, the water readily flows through the narrow slots which separate the fins, as well as through the central orifice. At higher pressures, however, the thin fins deform and gradually close off the slots therebetween, through which water will flow at the lower pressures. As a consequence, I am able to substantially increase the flow at such lower pressures by, in effect, increasing the effective size of the orifice, in that the liquid is permitted to flow through the slots as well as through the orifice thereby raising the flow volume to the same level as that reached at higher source pressures. At higher pressures, the fins deform and close off the slots and the disc in general is compressed so that the main orifice is diminished, thereby reducing the size of the path through which the liquid may flow and controlling that flow at a uniform volume.
Thus, it is an object of my invention to provide a flow washer which will permit essentially equally high volumes of flow therethrough at low source pressures as at high source pressures.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a plan view of my novel flow washer as viewed from the outlet side;
FIG. 2 is a vertical sectional view taken through one of my flow washers mounted in functioning position within a conduit, to effectively regulate the flow volume therethrough.
FIG. 3 is a chart diagram illustrating the flow volumes at varying source pressures through flow washers as heretofore known; and
FIG. 4 is a chart diagram illustrating the flow volumes at varying source pressures through my new flow washer.
DETAILED DESCRIPTION OF INVENTION
The preferred embodiment of my invention is shown in FIGS. 1-2, herein. As shown, it is comprised of a flow-control member in the form of a disc 5 having an axially extending orifice 6 which is defined by a plurality of radially extending fins 7. These fins 7 are separated by slots 8 which are preferably of uniform width. As shown, the fins 7 are carried by an outer annular supporting wall 9 which has radial dimensions approximating those of the fins 7, and which supports the fins 7 at its inner diametrical surface. The free inner end portions of the fins 7 are radiused slightly adjacent the inlet side 10 of the disc as at 11 to produce a more uniform flow.
FIG. 2 shows a conduit 12 having a groove or flow washer seat 13 formed therein to receive and hold such a flow control member, the arrows showing the direction of flow therethrough. As shown, the conduit is beveled at 45° as at 14, 15 at opposite sides of the disc and is comprised of sections 16, 17 which are secured together in any simple conventional manner (not shown). Such connections are conventionally utilized on conduits where there is need for such flow control as in wash machines, shower heads, etc.
Also, as shown in FIG. 2, the orifice defining portions of the disc 5 adjacent its outlet side 18 increase slightly in radius at a 45° angle as at 19 and then extend parallel to the axis of the orifice again as at 20. This increase in radius is provided to insure that any material left at the parting line will be located outside the flow of liquid therethrough and thus will not disrupt the flow stream.
The disc 5 is preferably made of a flowable-under-pressure, flexible, resilient elastomeric or plastic material. Among such materials are an ethylene propylene diene monomer, a silicone, or a nitrile. The material should have a hardness range of 30-95 durometer Shore A, preferably 50-70 durometer Shore A. The material is highly resistant to deterioration which otherwise may result from prolonged periods of time within water.
The market demand is principally for flow washers having an outer diameter of 0.680 inches, which is standard in that 85-90% of the flow washers currently sold are of this dimension.
There is a limited demand for flow washers having O'D's as low as 0.300 inches and some may go as low as 0.200 inches. The bulk, however, have O'D's approximating 0.680 inches which is the dimension of the disc 5 shown herein. The axial dimensions of the disc 5 are preferably within a range of 0.095-0.150 inches.
The radius of the orifice 6 may and does necessarily vary, depending upon the flow volume desired. I prefer, however, to maintain the length of the fins 7 at or about 0.100 inch and the radial dimensions of their supporting annular wall 9 at the same dimension. Thus, a disc having a 0.100 radius orifice will have a 0.300 overall radius, a disc having a 0.150 inch orifice radius will have a 0.350 inch overall radius, and a disc having an orifice with a 0.200 inch radius will have an overall radius of 0.400 inches.
As shown, the slots 8 which are cut in the disc 5 are 0.012 inches in width. They are preferably uniform in width within a range of 0.010-0.020 inches, and extend radially as shown. The preferred width range is 0.0125 to 0.0165 inches. The slots define the fins 7 therebetween, the latter having dimensions of 0.002-0.007 at their inner free end tips and substantially wider dimensions at their base, as shown.
It will be noted that the radial length of the fins 7 approximates the radial dimensions of outer wall 9 as well as the radius of the orifice 6. The supporting wall 9 may be thicker but should not be lesser in radial dimensions than those of the fins. The lengths of the fins 7 are preferably within a range of 0.070-0.130 inches.
The slots 8 can be cut through a molded preform disc 5, made of one of the materials hereinbefore defined. The fins 7 and the slot 8 must be narrow as defined, in order to function properly. It is impossible however, to cut such slots by mechanical means because the radially deformable material from which the disc is made will flow. I have found, however, that through the use of a Laser beam, I can cut such narrow slots and define such narrow fins. It is impossible to mold such fins because the portions of the mold which would define the same will collapse at standard molding pressures.
It will be readily seen that at low pressures, the slots 8 remain defined, with the result that a greater volume of liquid may pass through the orifice 6 and slots 8 of the disc then could otherwise flow through only its orifice. As the pressures raise, however, the fins 7 deform and close off the slots 8 so that all of the liquid must pass through the disc orifice. As the pressure mounts, the disc deforms further to restrict the orifice itself, in the same manner as heretofore occasioned in the use of conventional flow washers. As a result of the above action, such a flow-washer produces a uniform flow volume over a wider range of pressures, as shown by the charts of FIGS. 3 and 4. This is particularly evident in the lower pressure ranges where there presently is the greatest need for improved performance.
Reference to FIG. 3 shows the flow volume in gallons per minute when using a flow washer commonly in use today and prior to my invention. It will be seen that at pressures of 45 p.s.i., and greater, the flow is fairly uniform at 6 gallons per minute. Below 45 p.s.i., however, the flow volume drops off markedly so that at 20 p.s.i. it permits only 5 gallons per minute and at 15 p.s.i., it permits only 4.5 gallons per minute.
Reference to FIG. 4 shows the flow volume of my new flow washer at such low pressures at substantially higher levels. Thus, at 20 p.s.i., there is a flow of 7 gallons per minute and at 15 p.s.i. there is a flow of 6.7 gallons per minute. At 20 p.s.i., and for all pressures thereabove, there is a uniform flow of approximately 7 gallons per minute.
From the above, it can be seen that I have provided a flow washer of new design and material which markedly increases the flow of liquid permitted therethrough at the lower end of the pressure level range of conventional city water sources. This is particularly important for use wherein valves are coordinated with timers to control the length of time a valve is opened, such as in washing machines, where a predetermined volume of water needed. This is also of particular value in irrigation, wherein currently efforts are being made to greatly reduce the pressures needed, to 30 p.s.i. in order to conserve energy.
In considering the invention, it should be remembered that the present disclosure is illustrative only and the scope of the invention should be determined by the appended claims. | A flow washer in the form of a disc constructed of flowable-under-pressure, flexible, resilient material and having a plurality of closely spaced thin fins extending radially inwardly from an outer wall and terminating short of the disc's center to cooperatively define an axial orifice inwardly thereof. A method of making the flow washer is also disclosed. | 5 |
BACKGROUND OF THE INVENTION
The invention relates to an electronic sewing machine for electronically storing stitch control data which are sequentially read out with a timing pulse produced from a pulse generator operated in synchronism with rotation of an upper drive shaft of the sewing machine, to thereby control a stitch forming device. More particularly, the invention relates to a pattern varying device of the electronic sewing machine which is operated to control the transmission ratios between a data storing memory and the stitch forming device of the sewing machine as to vary the stitch width of a desired number of selected patterns with a predetermined variation rate for either progressively increasing or progressively reducing the stitch width of a series of such patterns.
According to the conventional electronic sewing machine, it is possible to vary or modify a pattern or a number of sequential patterns by manually adjusting a stitch width adjusting dial and a feed adjusting dial. However, such adjusting modes or values are determined during the production of the sewing machine at the factory, and therefore the variations or modifications of a pattern are limited. Moreover, when a number of sequential patterns is to be varied or modified with respect to a number of combined patterns, the machine operator is required to interrupt the running of the sewing machine each time one pattern is stitched so as to manually adjust the stitch width or feed amount for the next pattern. Such a manual operation is troublesome, and remarkably decreases the stitching efficiency.
SUMMARY OF THE INVENTION
An object of the present invention is to eliminate the aforesaid defects and disadvantages of the prior art sewing machines. To the achievement of this object, the sewing machine of the present invention substantially comprises: a number of pattern selecting switches selectively operated to produce a different pattern signal; a first electronic memory storing stitch control data for different patterns to be stitched; a pulse generator operated in synchronism with rotation of an upper drive shaft of the sewing machine to produce a timing pulse; addressing means operated in response to produce a timing pulse; addressing means operated in response to the timing pulse to address the first memory on the basis of the pattern signal so as to sequentially read the stitch control data from the memory for controlling a stitch forming device to produce a selected pattern of stitches; a second electronic memory for memorizing a selected number of pattern signals in a desired order for designating the initial address of the first memory; counter means operated to memorize the pattern signals in the second memory in a desired order and to indicate the total as well as the ordinal numbers of the pattern signals stored in the second memory; and calculating means for storing at least one predetermined calculating formula and being responsive to the total and the ordinal numbers of the pattern signals to modify the stitch control data by the calculating formula, to thereby control the operation of the stitch forming device with predetermined variation rates, wherein a desired number of patterns are successively produced with each pattern having a stitch width of a specific variation rate which results in a pattern as a whole having a progressively increasing or reducing variation rate.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a block diagram of a control circuit in accordance with the present invention;
FIG. 2 shows the patterns which are produced by the present invention;
FIG. 3 shows a control flow chart of the present invention;
FIG. 4 shows a control circuit of the present invention; and
FIGS. 5 and 6 each show a control time chart of the present invention.
DESCRIPTION OF PREFERRED EMBODIMENTS
Referring now to FIGS. 1-6 of the drawing, and more particularly to FIG. 1, there is shown a key board KEY including: pattern selecting switches selectively operated to produce a pattern data, a memory switch operated to store a number of patterns as a unit in an electronic memory, switches selectively operated to vary the unit of patterns, a machine controller switch operated to control the rotation speed of a machine drive motor, etc. PM is a memory for storing a number of the pattern data in a predetermined order as a unit of patterns. SM is another memory for storing stitch control data for different patterns, the initial addresses of which are each designated by the memory PM.
The memory SM is operated to produce a stitch control data each time it receives a timing pulse signal generated from a pulse generator which is operated in synchronism with the rotation of an upper drive shaft of the sewing machine, and to produce an end signal at the completion of each pattern. PON is a pattern order designating device for detecting the order of each pattern each time the memory SM produces the end signal and for holding the detected pattern order until the memory SM produces the next end signal. PVG is a pattern variation rate generating device for receiving a pattern variation rate designating signal from the key board KEY, the total number of memorized patterns from the pattern number storing memory PTN, and an ordinal of each pattern from the pattern order designating device PON.
The pattern variation generating device PVG is provided to vary the transmission ratio between the memory SM and a stitch forming device DV. The device PVG is operated in response to the pattern variation ratio designating signal to calculate the transmission ratio by means of a memorized calculation formula with a number of patterns to be a parameter and with the ordinal of each pattern to be variable. PVA is a multiplication device for receiving the stitch control data from the memory SM and the transmission ratio from the pattern variation rate generating device PVG, and multiplying the stitch control data by the transmission ratio and transmitting the output to the stitch forming device DV. Thus, the stitch forming device DV is operated to produce a pattern by a modified stitch control data, to thereby vary the size of each pattern of the sequential patterns.
FIG. 2 shows examples of the patterns which are produced by the invention. FIG. 2(a) is a unit pattern produced by the original data stored in the memory SM via a laterally swingable needle, while a fabric is vertically transported with a constant feeding pitch. FIG. 2(b) is a diagrammatic representation of calculation formula stored in the pattern variation rate generating device PVG for defining the maximum width of stitches for the respective patterns. The calculation formula is selected at the key board KEY. FIG. 2(c) shows another unit pattern of the same patterns comprising the pattern shown in FIG 2(a) which is produced by application of the calculation formula shown in FIG. 2(b). FIG. 2(d) shows yet another unit pattern comprising different patterns which is also produced by application of the aforesaid calculation formula, each pattern comprising substantially the same number of stitches.
FIG. 3 is a flow chart of the block diagram of the control circuit shown in FIG. 1. When a control power source is applied, the program is started from the START. The pattern progress number (na) is initially set to 1 by the pattern order designating device PON. The key board KEY is read, and a desired number of patterns (nt) is stored in the pattern number storing memory PTN. If the pattern variation mode No. 1 is designated from the pattern variation modes N, the end of the initial component pattern (completion of one cycle) is discriminated. This discrimination depends upon if the pattern order designating device PON receives the end signal from the stitch control data storing memory SM. If the initial pattern is not yet finished, the pattern variation rate generating device PVG calculates the variation rate of the initial pattern.
In this case, the pattern variation mode is number 1 as shown in FIG. 2(b). The variation rate calculation formula is KNA=NA/NT, provided the maximum width of the pattern (maximum width of the pattern in FIG. 2(b) is 1, the total number of the patterns is NT, the pattern progress number is NA, and the variation rate of each pattern is KNA. Therefore, if NA is 7, KNA=1/7 is the variation rate of the initial pattern in accordance with the pattern in FIG. 2(c). Then, the multiplication device TVA multiples the switch control data of the memory SM by the pattern variation rate with respect to the initial pattern to be stitched, to thereby reduce the original control data into 1/7 with respect to the stitch width of the initial pattern. The program repeats the progress from data read by KEY until the pattern is stitched up. Upon completion of the initial pattern, the progress number NA is added with number 1 to form a new NA, and the second pattern is which is not shown in FIG. 3, stitched in the same manner. When NA comes to NT the next pattern is NA+1. Thus, a series of patterns is repeatedly stitched. If the pattern selection is not accompanied by the pattern variation rate designation numbers 1 or 2, the variation rate KNA is 1 and the selected pattern or patterns are produced in accordance with the original stitch control data of the memory SM. In reference to FIG. 4, which shows a control circuit represented by the block diagram of FIG. 1, SW1 denotes a number of pattern selecting switches which form a part of the keyboard KEY in FIG. 1 and selectively operated to cause an encoder E to produce a 3-BIT code signal of a selected pattern to a latch circuit L1. Vcc is a positive control power source. R1 denotes a number of pull-up resistors. MM1 is a monostable multivibrator circuit for receiving a signal from the pattern selecting switches SW1 through a NAND circuit and having an output terminal Q for giving the signal to the trigger terminal Cp of the latch circuit L1, so that the latch circuit Li may latch the code signal of a selected pattern. RAM is an electronic random-access memory, corresponding to the pattern comprising memory PM in FIG. 1, and having an input IN for receiving the data from the latch circuit L1, an address input (ad) for designating a memory column for the received data, a mode terminal R/W for designating the writing of the data in the designated memory column, and an output OUT for producing the data in accordance to the read-out designation of the mode terminal R/W.
ROM is an electronic read-only memory, corresponding to the stitch control data storing memory SM in FIG. 1, for storing the stitch control data of various patterns to be stitched. The memory ROM has address input terminals A0-A7, of which the terminals A5-A7 receive the encoded signal, which is selected at the pattern selecting switches SW1, directly or indirectly from the output OUT of the memory RAM. S2 is a selected pattern memorizing switch forming a part of the key board KEY. The switch S2 is operated to produce a low level signal to operate a monostable multivibrator circuit MM2, which has a true side output terminal Q connected to the input of a delay circuit TD1.
An AND circuit AND1 receives the true side output Q of the monostable multivibrator circuit MM2 and the complement side output Q of the delay circuit TD1, and has an output connected to the input side of a NOR circuit NOR1. R2 is a pull-up resistor. The NOR circuit NOR1 receives the output Q of the monostable multivibrator circuit MM1 and has an output connected to the mode terminal R/W of the memory RAM, so that the output of the latch circuit L1 may be written or rewritten in the memory RAM each time the switch SW1 or SW2 is operated. Namely, when the switch SW1 or SW2 is not operated, the terminal R/W is maintained at a high level for normally giving the data read-out order. On the other hand, each time the switch SW1 or SW2 is operated, the terminal R/W becomes temporarily a low level giving the data write-down order. After a counter CT advances the address of the memory RAM by operation of the switch SW2, the data from the latch circuit L1 is written in the new addresses of the memory RAM by operation of switch SW1. If switch SW1 is repeatedly and solely operated without operation of the switch SW2, the data is rewritten each time a different switch SW1 is operated.
The counter CT corresponds to the pattern order designating device PON in FIG. 1, and is reset when the control power source is applied. The counter CT has a count-up terminal Up connected to the true side output terminals Q of the monostable multivibrator circuit MM2 and connected to the delay circuit TD through an AND circuit AND2 and an OR circuit OR1, and for counting subsequent to the operation of the switch SW2. A latch circuit L2 corresponds to the pattern number storing memory PTN in FIG. 1, and has an input IN for receiving the counting signal of the counter CT and has an output OUT connected to the pattern number input terminal (nt) of the pattern variation rate generating device PVG which has a pattern progress input (na) connected to the output OUT of the counter CT.
The latch circuit L2 has a trigger terminal Cp connected to the selected pattern memorizing switch SW2 through an AND circuit AND3 for receiving the complement side output Q of the monostable multivibrator circuit MM2 and connected to the true side output Q of the delay circuit TD1 through an OR circuit OR2 and a monostable multivibrator circuit MM3, so as to latch the counting up signals of the counter CT which is operated by operation of the switch SW2. SW3 aand SW4 are pattern variation mode designating switches, each comprising a part of the key board KEY in FIG. 1. Such switches may be employed in number as shown by "N" number of switches in FIG. 3. R3, R4 and R5 are pull-up resistors.
AND circuits AND4, AND5 each have one input terminal which are a high level when the switches SW3 and SW4 are operated, respectively, and each have another input terminal connected to the output Q of a flip-flop circuit FF1, which is set by the operation of the monostable multivibrator circuit MM2 when the pattern number memorizing switch SW2 is operated. Circuits AND4, AND5 each have an output terminal connected to the pattern variation mode designating inputs No. 1, No. 2, respectively, of the pattern variation rate generating device PVG, and are made effective when the switches SW3, SW4 are operated after the switch SW2 is operated. TB is a timing buffer having a reset terminal R connected to the output of the NOR circuit NOR1. Each time the switches SW1, SW2 are operated, the output of the timing buffer TB becomes 0, to thereby make 0 the address input terminals A0-A4 of the memory ROM connected to the output of the timing buffer TB. The timing buffer TB has a trigger terminal Cp connected to a pulse generator PG which is operated in synchronism with the rotation of the upper drive shaft of sewing machine (not shown herein) to produce a timing pulse per rotation of the upper drive shaft. Thus the timing buffer TB latches the address signals B0-B4 of the memory ROM to advance the address of the memory per rotation of the upper drive shaft. The relation between the memory ROM and the timing buffer TB is described in detail in U.S. Pat. No. 4,086,862 of the same applicant and which is incorporated herein by reference.
The memory ROM has a needle control signal output D B and a feed control signal output D F connected to the input sides of the multiplication devices PVA1, PVA2, respectively. PVA1, PVA2 have other input sides for receiving, through a switching device CD, the needle swing variation rate KB and the feed variation rate KF, respectively, produced by the pattern variation rate generating device PVG, to the calculations DB×KB and DF×KF. The resulting output of PVA1, PVA2 are applied to the stitch forming device DV. The switching device receives the stitch adjusting signals KB' and KF' besides the needle and feed variation rate signals KB, KF, which are separately controlled by the conventional stitch adjusting device, and is selectively operated by the signal from an OR circuit OR3, which receives the outputs from the AND circuits AND4, AND5, to make selectively effective the signals KB, KF and the signals K B ', K F '. When the switches SW3, SW4 are closed, i.e. when a varied combination of patterns is selected, the signals KB, KF are made effective. On the other hand, when the switches SW3, SW4 are opened, i.e. when the normal pattern stitching is selected, the signals X B ', K F ' are made effective.
SW5 is a controller switch comprising a part of the key board KEY, and is closed when a machine motor speed control controller is operated. The controller switch SW5 is operated to produce a low level signal to actuate a monostable multivibrator circuit MM4. Then the monostable multivibrator circuit MM4 gives the true side output Q to the set terminal S of a flip-flop circuit FF2 to set the latter. The flip-flop circuit FF2 has a terminal J grounded to be a low level, a terminal K connected to the true side output terminal Q thereof and a trigger terminal CP is connected to the output terminal Q of the monostable multivibrator circuit MM1, so that the flip-flop FF2 may be reset by the low level signal of the monostable multivibrator circuit MM1.
The counter CT has a reset terminal R connected, through an OR circuit OR4, to the output of a delay circuit TD2 which is operated by the complement side output of the flip-flop circuit FF2, and is connected to the output of an AND circuit AND6 having its input connected to the output Q of the monostable multivibrator circuit MM$. The counter CT is reset when the controller switch SW5 is operated after the pattern selecting switch SW1 is operated. The true side output Q of the flip-flop circuit FF2 is connected to the reset terminal R of the monostable multivibrator circuit MM2, and to one input terminal of AND circuit AND7 and of AND circuit AND8.
The address signal A0-A4 of the memory ROM provides 0 for the initial stitch, and then the monostable multivibrator circuit MM5 is operated through the NOR circuit NOR2. The AND circuit AND7 has another input connected to the output Q of the monostable multivibrator circuit MM5, and has the output connected to the count-up terminal Up of the counter CT through an OR circuit OR1, so that the counter CT may advance the count each time a new unit of patterns starts to be stitched. The AND circuit AND8 has another input connected to the output Q of the monostable multivibrator MM1 so as to reset the counter CT through the OR circuit OR4 when the pattern selecting switch SW1 is operated after the controller switch SW5 is operated. At the same time, the latch circuit L2 latches the value 0 of the counter CT through the OR circuit OR2 and the monostable multivibrator circuit MM3, and the flip-flop circuit FF1 is reset.
Exclusive OR circuits ExOR1-ExOR4 compare the output signal of the counter CT and the output signal of the latch circuit L1 with respect to the bits of these output signals. If all the bits of the output signals are in accord with each other, the exclusive OR circuits operate a monostable multivibrator circuit MM6 through a NOR circuit NOR3. The output Q of the monostable multivibrator circuit MM6 resets the counter CT through the OR circuit OR4, to thereby make 0 the pattern number progressing input terminal (na) of the pattern variation rate generating device PVG, so as to meet the initial stitch of a combination of patterns.
Referring particularly to FIGS. 5 and 6, the operation of the control circuit will now be explained; if one of the pattern selecting switches SW1 is pushed, a low level signal is produced to operate the monostable multivibrator circuit MM1. Then the latch circuit L1 latches a new data NEW in place of the old data OLD, and the memory RAM is written with the new data NEW in place of the old data OLD. At this time, the address input (ad) is n-1. With the operation of the pattern selecting switch SW1, the flip-flop FF2 is reset, and the AND circuit AND8 nullifies the signal of the pattern selecting switch SW1. The counter CT is therefore not reset and receives no counted input.
Then if the selected pattern number memorizing switch SW2 is pushed to store the selected pattern so as to form a series of patterns, a low level signal is produced to operate the monostable multivibrator circuit MM2 which will then produce a pulse signal. Subsequently, the delay circuit TD1 is operated to produce a pulse of the same width as the pulse width of the monostable multivibrator MM2. With the production of the pulses, the AND circuits AND1, AND2, AND3 produce a pulse one after another as is shown in FIG. 6. With the high level signal of the AND circuit AND1, the mode terminal R/W of the memory RAM becomes a low level, and the same data is memorized again at a column designated by the address n-1. With the subsequent high level signal of the AND circuit AND2, the counter CT is operated to count up and the address (ad) becomes (n). With the subsequent high level signal of the AND circuit AND3, the latch circuit L2 latches the output data (n) of the counter CT. Thus, each time the switch SW2 is operated, the AND circuits AND1, AND2, AND3 are operated to write the data in the memory RAM, advance the address (ad), and latch the same data in the latch circuit L2. Thus, a desired number of the same patterns are stored in the latch circuit L2. If another one of the pattern selecting switches SW1 is pushed after the pattern number memorizing switch SW2 is pushed, a series of different patterns are memorized.
Then if the pattern variation designating switch SW3 or SW4 is pushed, the pattern variation No. 1 or No. 2 is designated to the pattern variation rate generating device PVG because the flip-flop circuit FF1 is already set. The switching device CD is then operated to transmit to the multiplication devices PVA1, PVA2, the needle swing variation rate signal K B and the feed variation rate signal K F , respectively, of the pattern variation rate generating device PVG. Then if the controller not herein shown is operated to close the switch SW5, the flip-flop circuit FF2 is set, the counter CT is reset and the address (ad) becomes 0. This address corresponds to the initial address of the stitch control data of the pattern selected by the switch SW1, namely the address n-1 in FIG. 6.
The sewing machine needle is brought to the initial stitching position of the pattern by the stitch forming device DV which is operated by the product KB DB, KF DF of the output data DB, DF and the output data KB, KF. In this case, the data DB, DF are read from the memory ROM with the condition that the address signals A7-A5 of A7-A0 are designated to the initial address of the stitch control data and the other address are 0. This corresponds to na=1 in FIG. 3 representing the stitching progress of pattern. In this case, the pattern variation rate Kna corresponds to the needle swing variation rate KB. It is also possible to apply the same calculating formula to the feed variation rate KF.
As the upper drive shaft of the sewing machine is rotated, the pulse generator PG produces a timing pulse. With the first timing pulse, the memory ROM is initially addressed and produces the stitch control data D B , D F , and at the same time produces the addressing data B4-B0 which is latched in the timing buffer TB and is applied to the address inputs A4-A0 for reading out the next stitch control data D B , D F . In this manner, the pattern stitches are formed as the upper drive shaft is rotated. When the data D B , D F is produced for the last stitch of the initial pattern of the sequential patterns, the simultaneous addressing data B4-B0 is 0. Then the counter CT starts to count up to designate the initial address of the second pattern. In this manner, a number of patterns are produced one after another until the last pattern is finished up. If the counter CT counts up the last number of the patterns which are stored in the latch circuit L2, the monostable multivibrator circuit MM6 is operated to reset the counter CT, which will then designate the initial address of the initial pattern of the sequential patterns. Thus, a memorized number of sequential patterns are repeatedly produced.
If the pattern selection is implemented with the pattern selecting switches SW1 and the memorizing switch S2, and without operation of the pattern variation rate designating switch SW3 or SW4, the switch adjusting signals KB', KF', which are variable by operation of the normal stitch adjusting dials, are made effective in place of the needle swing variation rate signal KB and the feed variation rate signal KF. If the pattern selection is implemented without operation of the pattern memorizing switch SW2, the counter receives no input and therefore a pattern selected by the switch SW1 is repeatedly produced.
While the invention has been illustrated and described as embodied in an electric sewing machine, it is not intended to be limited to the details shown, since various modifications and structural changes may be made without departing in any way from the spirit of the present invention.
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. | Disclosed is an electronic sewing machine for modifying a stitch pattern with stitch forming instrumentalities, including a first memory for storing stitch control data used to control said stitch forming instrumentalities, a plurality of pattern selecting switches selectively operable for producing a different pattern signal for addressing the first memory to sequentially read the stitch control data, a second memory for storing a selected number of pattern signals, each one of the selected number of pattern signals designating an initial address of the first memory, a counter for counting the total and ordinal number of the pattern signals stored in the second memory, and a calculating device for storing at least one calculation formula for selecting a predetermined variation rate, the calculating device being responsive to the total as well as ordinal numbers of the pattern signals to modify the stitch control data read from the first memory for controlling the stitch forming instrumentalities. | 3 |
BACKGROUND OF THE INVENTION
This invention relates broadly to the art of sinks, and more particularly to sink cabinets, and to apparatus for protecting sink cabinets and houses from water damage.
It has been normal practice since around 1940 to 1950 to construct sink assemblies having enclosed cabinets positioned below sink bowls, for supporting the sink bowls. Such sink assemblies have been found to be more aesthically pleasing than "bare" sink bowls and have also had the practical advantage of "using" what is otherwise wasted space below the sink bowls. However, such structures magnify problems which theretofore were not significant.
A significant problem involved with such sink assemblies is that water often gets into the enclosures below the sink bowls and causes damage. There are various sources of water, for example: (1) it leaks through cabinet tops around the sink bowls, and other openings in the cabinets; (2) the drain pipes of the sink bowls spring leaks; and, (3) condensation takes place on bottoms of the sink bowls and on sink drain pipes in the cabinet enclosure. This water problem is enhanced by a lack of visibility for sink users of the enclosed spaces under the sink bowls. Thus, water damage often occurs without users realizing that water is accumulating below the sink bowls. Such water damage includes mildew, rotting, and damaged articles stored in the cabinets below the sinks. In addition to damaging the cabinets and houses, this water damage sometimes makes it difficult to keep the cabinets clean and neat.
Thus, it is an object of this invention to provide a sink assembly whose cabinet enclosure and whose house in which the sink assembly is mounted are protected from water damage.
It is also an object of this invention to provide a sink assembly whose enclosed cabinet can be kept neat and clean even though water may get into the enclosure space on occasion.
Further it is an object of this invention to provide a sink assembly which is not unduly expensive to manufacture.
Finally, it is an object of this invention to provide a method of protecting sink assembly cabinet enclosures, and houses generally, from water which is sometimes discharged at sinks.
SUMMARY
According to principles of this invention, a sink cabinet liner is located in a cabinet enclosure below a sink bowl to catch water falling therein from leaks through the cabinet, leaks in the bowl drain pipe, condensation, etc. The liner forms a bottom surface of the cabinet on which goods can be stored. The liner has a drain therein for draining water accumulated by the liner outside of the house.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular description of the preferred embodiments of the invention, as illustrated in the accompanying drawings in which like reference characters refer to the same parts throughout different views. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating principles of the invention.
FIG. 1 is an isometric view of a sink assembly of this invention having a cabinet-enclosure liner;
FIG. 2 is a front cut-away view of a sink assembly of this invention having a different type of liner drain system than the liner drain system of the FIG. 1 embodiment; and,
FIG. 3 is a side cut-away view of a sink assembly of this invention having yet a third type of drain system.
DESCRIPTION OF PREFERRED EMBODIMENTS
FIG. 1 depicts a sink assembly 12 including a cabinet 14, a sink bowl 16, a water faucet 18, a sink-bowl drain 20, and a cabinet liner 22.
The cabinet 14 is supported by a house floor 24 and, in turn, supports the sink bowl 16 and the water faucet 18 in holes 26 and 28 respectively which extend through an upper surface 30 of the cabinet 14. The sink bowl 16 extends through the hole 28 in the upper surface 30 down into an enclosed space 32 of the cabinet 14 where it communicates with the sink-bowl drain 20. In this respect, there is a drain hole 34 in the sink bowl 16 through which water drains into the sink-bowl drain 20. The sink-drain 20 thereafter extends through an opening 36 in the back of the cabinet 14 and finally into a house drain stack 38 for being exhausted outside of a house in which the sink assembly 12 is located. Doors 39 allow access into the space 32 from the front of the cabinet 14.
The cabinet 14 includes a floor 40 on which the cabinet liner 22 sits. The cabinet liner 22 is, in a preferred embodiment, constructed of a pliable PVC molded plastic. Such a plastic is substantially chemical- and heat-resistant and flame retardant, and, because of its flexibility, can be retrofitted more easily into existing sink-assembly cabinets. The cabinet liner 22 has a drain pan 42 from which vertical front, back, and side walls 44 a, b, c and d extend. The front wall 44a has a height of about 11/2 inches so that easy access can be had to items (such as boxes of soap, brushes, etc.) which are stored on the drain pan 42. However, the back wall 44c is relatively high, so that it can catch water which sprays rearwardly thereagainst. In this respect, it is best to make the back and side walls 44c, 44b and 44d as high as possible to catch laterally squirting water. In the depicted embodiment the side walls 44b and d taper downwardly from the back wall 44c so as to match the height of the front wall 44a at the transition therebetween. The back wall 44c is approximately 15 inches high, however, it can be higher and it is not necessary that the side walls 44b and d be tapered.
The liner 22 is sized such that its back and side walls 44c, b and d are immediately adjacent to side and back walls of the cabinet 14 so as to cut down very little on the storage capacity of the cabinet 14.
The outside periphery of the drain pan 42 is raised above the cabinet floor 40 by means of legs 46. The drain pan 42 tapers downwardly toward a drain-hose nipple 48 which defines a drain hole 50. The drain hole 50 communicates with a second drain pipe 52 which, in turn, leads into the house drain stack 38. The second drain pipe 52 can be metal, or it can be plastic. This hose can also be of a flexible nature so that it can more easily be retrofitted to existing sink cabinets. The fact that the drain pan 42 is raised above the cabinet floor 40 by the legs 46 is beneficial in that free air circulation is allowed between the bottom of the drain pan 42 and the cabinet floor 40 so as to avoid moisture build-up therebetween. Further, by raising the periphery of the drain pan 42, liquid flow toward the drain hole 50 is thereby enhanced.
In a preferred embodiment, the cabinet liner 22 is sold with higher sides 44 than are shown in FIG. 1 and a user simply cuts them to an appropriate size for fitting into a sink cabinet. In this manner, one can have the highest liner size permissible for a particular sink liner to thereby aid in catching laterally sprayed water.
The sink assembly of FIG. 2 is substantially the same as the sink assembly of FIG. 1 with the exception that, in the FIG. 2 embodiment, a second drain pipe 54, rather than leading directly into a drain stack 38, is arranged to extend downwardly to a basement floor drain 58. Thus, any water drained from a cabinet liner 22 of the FIG. 2 arrangement drains into the floor drain 58 of a basement floor 56. In this respect, it should be realized that the flow of water from the cabinet liner 22 will not normally be great. This liner is intended to take emergency water which leaks, or condenses from the sink bowl 16 and the sink-bowl drain 20.
In FIG. 3, a second drain pipe 60 of the cabinet liner 22 does not connect with the house drain stack 38 at all, but rather extends through an exterior wall 62 of a house in which the sink assembly 12 is located to deposit water on the ground 64 outside of the house. Again, the flow of water from the liner 22 will not normally be great, and such an arrangement can be tolerated.
It will be appreciated by those skilled in the art that the sink assembly described herein, having a drained cabinet liner, overcomes various shortcomings of prior-art enclosed sink-supporting-cabinet assemblies. The liner prevents potential water damage and allows the cabinet interior to be kept cleaner and neater than was normally the case. The sink assembly described herein is relatively uncomplicated in structure, and inexpensive to install.
While the invention has been particularly shown and described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention. In one embodiment, for example, the cabinet liner 22 does not include a drain. In this embodiment the liner must be wiped out with a cloth when it catches water. This embodiment of the liner has the advantage of being more portable than the liner with a drain. Such a liner can be easily added to an already existing kitchen cabinet without reducing the storage space of the cabinet, since the liner substantially fits the interior of the cabinet. | A sink assembly of a type including an enclosing cabinet (14) for supporting a sink bowl (16) from a floor (24) includes a liquid-impervious cabinet liner (22) supported by the cabinet (14) within an enclosed space (32) below the sink bowl (16) and its drain pipe (20) for catching water dripping from leaks and condensations. The sink liner (22) communicates with a second drain pipe (52) which exhausts water from the sink liner (22). The sink liner (22) is constructed so that its drain pan (42) is raised above a cabinet floor (40), with the drain pan (42) having tapered surfaces for accelerating flow toward the second drain pipe (52). | 4 |
RELATED APPLICATION DATA
This application is a continuation-in-part of U.S. application Ser. No. 08/314,204, filed Sep. 28, 1994, which is incorporated herein in its entirety by reference.
TECHNICAL FIELD
The invention is directed to the preparation of sulfur-containing organosilicon compounds useful as coupling agents in vulcanizable rubbers to enhance products made from them. In its preferred form, the invention improves the preparation of Ω,Ω'-bis (trialkoxysilylalkyl) polysulfides.
Sulfur-containing organosilicon compounds have found widespread use in a variety of rubber products in the last two decades. Uses include tire walls and bodies, rubber hoses, rubber belts, and numerous other rubber products. Depending on the formulation, selected properties of the rubber can be modified.
Since the early 1980's, automobile manufacturers have been encouraging the production of low-rolling-resistance tires. A number of sulfur-containing organosilicon compounds have been identified as useful in this regard. The improvements obtainable could be helpful in meeting federal fuel economy standards without sacrificing wet traction and wear. Silane polysulfide coupling agents, such as 3,3'-bis (triethoxysilylpropyl) tetrasulfide, have been proposed for use in low-rolling-resistance tires.
To achieve optimum effect, it has been found that each low-rolling-resistance tire should contain several ounces of this or another suitable silane.
There is a need for new processes to produce organosilane polysulfides effective for use in low-rolling-resistance tires, and other uses, in good yield to permit economical production of large quantities with controllable safety and environmental impact.
BACKGROUND ART
The art of manufacturing organosilane polysulfides is well established, with the art offering a variety of processing strategies.
Meyer-Simon, Schwarze, Thurn, and Michel disclose the reaction of a metal polysulfide with an Ω-chloroalkyltrialkoxysilane in U.S. Pat. No. 3,842,111. Example 2 shows the preparation of 3,3'-bis (triethoxysilylpropyl) tetrasulfide by reacting Na 2 S 4 with 3-chloropropyltriethoxysilane in absolute ethanol. The procedure for preparing the metal polysulfide is not exemplified, and the examples imply that this starting material is an isolated compound.
In U.S. Pat. No. 4,072,701, Pletka describes the preparation of sulfur-containing organosilicon compounds by first heating 3-chloropropyltrichlorosilane (Example 1) with ethanol, and then adding both sulfur and NaSH in the presence of alcohol. The reaction developed gaseous hydrogen sulfide in situ, but some of the sulfur therein was not recoverable (see, U.S. Pat. No. 4,129,585, col. 1, lines 32-34, in this regard). Therefore, the yields based on added sulfur tended to be low. Also, the use of NaSH is problematic due to its deliquescent nature and its tendency to oxidize to sulfate. The deliquescence is troublesome from the standpoint that it increases the risk that water will enter the reaction and cause hydrolysis of the alkoxide reactants.
After describing the above two patents in U.S. Pat. No. 4,129,585, Buder, Pletka, Michel, Schwarz and Dusing, describe a procedure for making the noted compounds without the production of gaseous hydrogen sulfide. The process entails reacting a suitable alkali metal alcoholate, e.g., sodium ethoxide, in preferably alcoholic solution with a desired Ω-chloroalkyltrialkoxysilane, a suitable metal hydrogen sulfide, and sulfur. The resulting product was purified by separating the salt formed and distilling off the alcohol. Again, the use of the metal hydrogen sulfide can be a source of water entering the system unless precautions are taken.
In U.S. Pat. No. 4,507,490, Panster, Michel, Kleinschmidt and Deschler, first prepare Na 2 S. Again, they employ a metal hydrogen sulfide but react it with an alkali metal, such as sodium, in a polar solvent, such as ethanol. This reaction is highly exothermic and evolves hydrogen gas. The process is said to eliminate the use of an alkali metal alcoholate solution, noting that its production requires such a great deal of time as to be industrially improbable. The Na 2 S is reacted with additional sulfur to form a desired polysulfide, preferably Na 2 S 4 . The polysulfide is then reacted with a desired Ω-chloroalkyl trialkoxysilane, e.g., Cl(CH 2 ) 3 Si(OC 2 H 5 ) 3 , to form the desired Ω,Ω'-bis (trialkoxysilylalkyl) polysulfide.
Janssen and Steffen, in U.S. Pat. No. 3,946,059, offer a distinct approach and criticize procedures of the type described above. They eliminate the production, and therefore separation, of salts formed in the above reactions by contacting a bis (alkylalkoxysilyl) disulfide with sulfur at a temperature between 100° and 200° C. This procedure, however, adds the difficulty of the high temperature processing and requires the initial preparation of bis-silyl disulfides by the reaction of sulfuryl chloride with silyl mercaptans.
While the possibility might appear to exist that commercial forms of alkali metal sulfides, e.g., sodium tetrasulfide, could be employed, this would not be practical. The commercial forms of sodium tetrasulfide include water which must be completely removed prior to contact with the alkoxylates. If water is present, the alkoxide is hydrolyzed and a polysiloxane polymer is formed. And, while Bittner, et al. teach in U.S. Pat. No. 4,640,832, the reaction of sodium salts with hydrogen sulfide in alcoholic solution, this route has been criticized as "quite inconvenient" (see Lichty at CA, 7, 2910 (1913)).
Thus, the prior art has found the use of hydrogen sulfide gas, the separation of sodium chloride and the preparation of metal alkoxylates to be problematic in the preparation of sulfur-containing organosilicon compounds, and did not recognize that there was possible a reaction scheme which efficiently and effectively combines all of them. The invention provides a process which combines these and still obtains high yields based on sulfur.
SUMMARY OF THE INVENTION
It is an object of the invention to provide improved processes for preparing sulfur-containing organosilicon compounds useful as coupling agents in vulcanizable rubbers.
It is a further object of a preferred aspect of the invention to provide improved processes for preparing Ω,Ω'-bis (trialkoxysilylalkyl) polysulfides useful in the preparation of a variety of rubber products, specifically including low-rolling-resistance tires.
It is a further and more specific object of the invention to prepare 3,3'-bis (triethoxysilylpropyl)tetrasulfide economically in high yield.
These and other objects are achieved by the invention which provides a process for preparing silane polysulfides, comprising:
(a) contacting hydrogen sulfide gas with an active metal alkoxide solution; and then
(b) reacting the product of step (a) with a slurried mixture of elemental sulfur and a halohydrocarbylalkoxysilane of the formula
Q--R--X
in which Q is ##STR1## and in which R 1 is an alkyl group of 1 to 4 carbon atoms or phenyl, and
R 2 is an alkoxy group with 1 to 8, preferably 1 to 4, carbon atoms,
a cycloalkoxy group including 5 to 8 carbon atoms, or a straight or branched chain alkylmercapto group with 1 to 8 carbon atoms,
wherein the various R 1 and R 2 groups can be the same or different,
R is a divalent hydrocarbyl group including 1 to 18 carbon atoms, and
X is a halogen,
to produce a compound of the formula
Q--R--S--R--Q
in which Q and R are as defined above, and n is an integer of from 2 to 9, preferably from 3 to 5.
The desired product is 3,3'-bis (triethoxysilylpropyl) tetrasulfide, represented by the formula
(C.sub.2 H.sub.5 O).sub.3 Si(CH.sub.2).sub.3 --S.sub.4 --(CH.sub.2).sub.3 Si(OC.sub.2 H.sub.5).sub.3,
and is prepared by a contacting an ethanol solution of sodium ethoxylate with hydrogen sulfide gas to produce a solution of sodium sulfide, and then reaction of the sodium sulfide so produced in a slurry with elemental sulfur and Cl(CH 2 ) 3 Si(OC 2 H 5 ) 3 and carrying the reaction to completion.
All parts and percentages in this description are on a weight basis and are based on the weight of the composition at the referenced stage of processing.
DETAILED DESCRIPTION
The invention, which relates to the preparation of sulfur-containing organosilicon compounds useful for a variety of purposes, especially as coupling agents in vulcanizable rubbers, will be described with special reference to the preparation of a preferred class of compounds, the Ω,Ω'-bis (trialkoxysilylalkyl) polysulfides.
Among this class of compounds are a large number of materials, including the various polysulfides listed below wherein the term polysulfide includes all of the di, tri, tetra, penta, hexa, hepta, octa, and nona-sulfides according to the following formulae:
bis (trimethoxysilylmethyl) polysulfides, bis (triethoxysilylmethyl) polysulfides, bis (dimethylethoxysilylmethyl) polysulfides, bis (tripropoxy-silylmethyl) polysulfides, bis (tributoxysilylmethyl) polysulfides, bis (tripentoxy-silylmethyl) polysulfides, bis (trihexoxysilylmethyl) polysulfides, bis (triheptoxy-silylmethyl) polysulfides, and bis (trioctyloxysilylmethyl) polysulfides;
3,3'-bis (trimethoxysilylpropyl) polysulfides, 3,3'-bis (triethoxysilylpropyl) polysulfides, 3,3'-bis (dimethylethoxysilylpropyl) polysulfides, 3,3'-bis (tripropoxysilylpropyl) polysulfides, 3,3'-bis (tributoxysilylpropyl) polysulfides, 3,3'-bis (tripentoxysilylpropyl) polysulfides, 3,3'-bis (trihexoxysilylpropyl) polysulfides, 3,3'-bis (triheptoxysilylpropyl) polysulfides, 3,3'-bis (trioctyloxysilylpropyl) polysulfides, and 3,3'-bis (methyldiethoxysilylpropyl) polysulfides;
4,4'-bis (trimethoxysilylbutyl) polysulfides, 4,4'-bis (triethoxysilylbutyl) polysulfides, 4,4'-bis (dimethylethoxysilylbutyl) polysulfides, 4,4'-bis (tripropoxysilylbutyl) polysulfides, 4,4'-bis (tributoxysilylbutyl) polysulfides, 4,4'-bis (tripentoxysilylbutyl) polysulfides, 4,4'-bis (trihexoxysilylbutyl) polysulfides, 4,4'-bis (triheptoxysilylbutyl) polysulfides, and 4,4'-bis (trioctyloxysilylbutyl) polysulfides;
5,5'-bis (trimethoxysilylpentyl) polysulfides, 5,5'-bis (triethoxysilylpentyl) polysulfides, 5,5'-bis (dimethylethoxysilylpentyl) polysulfides, 5,5'-bis (tripropoxy-silylpentyl) polysulfides, 5,5'-bis (tripentoxysilylpentyl) polysulfides, 5,5'-bis (tripentoxysilylpentyl) polysulfides, 5,5'-bis (trihexoxysilylpentyl) polysulfides; and
5,5'-bis (triheptoxysilylpentyl) polysulfides, and 5,5'-bis (trioctyloxysilylpentyl) polysulfides.
Similarly, the 6,6'-bis (trialkoxysilylhexyl) polysulfides; the 7,7'-bis (trialkoxysilylheptyl) polysulfides; the 8,8'-bis (trialkoxysilyloctyl) polysulfides; the 9,9'-bis (trialkoxysilylnonyl) polysulfides; the 10,10'-bis (trialkoxysilyldecyl) polysulfides; and the isomers of these are included. Indeed, this disclosure is meant to include, each of the individual compounds comprised of combinations of the various groups encompassed by the generic formula
Q--R--S--R--Q
wherein, Q, R and n are as defined above.
This description illustrates the production of the preferred compound, 3,3'-bis (triethoxysilylpropyl) tetrasulfide:
(C.sub.2 H.sub.5 O).sub.3 Si(CH.sub.2).sub.3 --S.sub.4 --(CH.sub.2).sub.3 Si(OC.sub.2 H.sub.5)3
by the process described above. At times in the following description, Et is used to designate an ethyl group and Me is used to designate a methyl group.
Preparation of the Active Metal Alkoxide
As noted above, the process can be used to prepare a large number of end products. For each of these it is necessary to start with an active metal and an alcohol. They may be prereacted to form an active metal alkoxide solution. The active metal alkoxide will have the formula M-R 2 , wherein M represents an active metal and R 2 is as defined above. Among the preferred active metals are those of the alkali metal group, especially sodium and potassium. The most preferred is sodium. However, among the other metals useful are lithium, rubidium and cesium. Among the preferred alkoxides are those containing methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, 2-methoxyethoxy or 2-ethoxyethoxy groups.
The prereaction, if performed, is carried out in a suitable organic solvent compatible with the alkoxide. In principle, any polar organic solvent can be employed that reacts with neither the alkali or other metal nor with the organic silicon compounds to form an undesired byproduct.
Preferably, the organic solvent is a linear or branched alcohol having 1 to 5 carbon atoms, e.g., methyl, ethyl, propyl, butyl or pentyl alcohol, as well as iso-propyl alcohol, iso-butyl alcohol and 2-methoxyethanol. Also suitable are cycloalkyl alcohols having 5 to 8 carbon atoms, e.g., cyclopentyl alcohol, cyclohexyl alcohol, cyclooctyl alcohol, phenyl or benzyl alcohol. It is useful to employ the alcohol which in each case corresponds to the R 2 group. In a given case, advantageously there can also be used a mixture of these alcohols, e.g., when different R 2 groups are used in a compound. Particularly preferred are methanol and ethanol, preferably in absolute form. In one preferred process, sodium metal is reacted with ethanol to form an ethanolic solution of sodium ethoxylate.
The reaction of active metal, e.g., sodium metal, and a suitable alcohol, e.g., ethanol, is preferably conducted with an excess of alcohol to produce a metal alkoxide, e.g., sodium ethoxide, solution. The following equation summarizes the reaction:
M+R.sup.2 H→MR.sup.2 +1/2 H.sub.2
The sodium or other metal should be maintained free of contact with moisture. The manufacture of sodium methoxide has been described by Arend (Arend, A. G., Perfumery Essent. Oil Record, 28, 372-75, 1947). The preferred sodium ethoxide reaction is similar to, but slower than, the sodium methoxide reaction.
The concentration of the sodium ethoxide solution may be as low as about 10 wt % and as high as its solubility limit, which is about 25 wt % at 25° C. A high concentration of sodium ethoxide is desirable, since better product yields for given reactor size are obtained. The typical concentration for commercially-available sodium ethoxide is about 21 wt %.
The H 2 S-Active Metal Alkoxide Reaction
H 2 S (hydrogen sulfide) gas is reacted with the active metal alkoxide (e.g., sodium ethoxide) in a suitable solvent (e.g., ethanol) to produce a suitable active metal sulfide, e.g., Na 2 S:
2 MR.sup.2 +H.sub.2 S→M.sub.2 S+2 R.sup.2 H
This reaction can be performed in production quantities of from about 50 to about 5,000 pound batches. Continuous and semi-continuous processes can also be employed. Preferably, the reaction is carried out with an excess of ethanol, typically charging the preferred sodium ethoxide raw material as a 21 wt % solution in ethanol. The preferred reaction between hydrogen sulfide gas and sodium ethoxide employs a molar feed ratio of the hydrogen sulfide to the sodium ethoxide of 1:2.
The reaction is conveniently conducted in a semi-batch mode. First, all of the metal alkoxide is added to the reactor. Then, the reactor contents are heated to a temperature effective for reaction, in the preferred case discussed, within the range of from about 40° to about 50° C., e.g., about 50° C. The hydrogen sulfide gas is then fed to the reactor. The hydrogen sulfide feed rate is not critical, typically it will be of the order of one hour, but will vary with equipment and batch size. At the end of the reaction, most of the active metal sulfide is in solution. However, some solid active metal sulfide particles may be present. In general, it is desirable to keep the system agitated until the next step.
Preferably, the reactor is maintained at a temperature between about 40° and about 60° C. during the hydrogen sulfide addition to avoid discoloration. The reaction necessitates some degree of cooling. After the hydrogen sulfide addition is completed, it is desirable to purge out the feed conduit with nitrogen to prevent draw back of liquid. After the purge, the kettle is preferably cooled, e.g., to about 25° C., and then vented to atmospheric pressure through a reflux condenser to trap out any ethanol vapors while maintaining the kettle blanketed with nitrogen gas.
The system is preferably equipped with a scrubber or absorber for capturing hydrogen sulfide emissions. Strong sodium hydroxide is a good scrubbing medium. The reaction is preferably conducted in a mechanically-agitated kettle to assure good gas-liquid mixing to facilitate the reaction of the hydrogen sulfide with the active metal alkoxide. The hydrogen sulfide gas is desirably fed subnatantly via a diptube or gas sparger located near or preferably below the agitator.
Stoichiometry is important. The desired ratio is one mole of hydrogen sulfide per two moles of active metal alkoxide, with a preferred accuracy of hydrogen sulfide addition being about ±3%.
Sulfur and Halohydrocarbyltrialkoxysilane Addition and Reaction
The process of the invention employs a halohydrocarbyltrialkoxysilane for reaction with sulfur and the reaction product prepared above. These compounds meet the general formula Q--R--X in which Q and R are as defined above and X is a halogen, typically chlorine, but bromine, iodine and fluorine compounds can be effective. In this formula, and therefore also in the final product, the hydrocarbyl group R signifies methylene as well as preferably n-propylene, i-butylene, or n-butylene, but can also be n-pentylene, 2-methylbutylene, 3-methylbutylene, 1,3-dimethylpropylene, n-hexylene, or n-decylene.
Illustrative compounds within formula Q--R--X are 3-chloropropyltriethoxysilane, 3-bromopropyltriethoxysilane, chloromethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyldiethoxymethylsilane, 3-chloropropylcyclohexoxydimethylsilane, 4-bromobutyldiethoxybenzylsilane, 4-chlorobutyltrimethoxysilane, 5-chloropentyldimethoxyphenylsilane, 3-bromo-i-butyltriethoxysilane, 3-chloropropyldimethoxy-p-ethylphenylsilane, 3-chloropropylethoxymethylethylsilane, 5-chloro-n-pentyldiethoxycyclopentylsilane, 3-bromopropyldimethoxycyclopentoxysilane, 3-bromo-2-methylpropyldimethoxy-cyclooctylsilane, 3-chloropropyldiethoxy-2-methoxyethoxy-silane, 3-chloropropyldibutoxymethylsilane, 3-bromopropylphenyloxydimethoxysilane, 3-chloropropyl-di-i-butoxy-2-methylphenysilane, 4-chlorobutyldimethoxybenzyloxysilane, 3-chloropropyltributoxysilane, 3-chloropropyldiethoxyamylsilane, and 3-chloropropyldiethoxy-p-methylphenylsilane.
Again here, as in the case of the inclusion of compounds meeting the definition of the formula for the end products, this disclosure is meant to include each of the individual compounds comprised of combinations of the various groups encompassed by the generic formula Q--R--X in which R and X are as defined above.
Preferred chloroalkylalkoxysilanes can be purchased or prepared according to any of the techniques available to those of ordinary skill in the art. One preferred practice is to prepare it by transesterification of Cl(CH 2 ) 3 Si(OMe) 3 .
In an alternative embodiment of the invention, the methoxy ester can be employed to form 3,3'- bis (trimethoxyalkoxysilane) polysulfide, and this product can then be converted to the ethyl or higher ester by transesterification in situ.
According to this embodiment, Cl(CH 2 ) 3 Si(OEt) 3 can be prepared by the following transesterification reaction, typically at a temperature of from about 70° to about 100° C. and atmospheric pressure using about 2000 ppm para-toluenesulfonic acid:
Cl(CH.sub.2).sub.3 Si(OMe).sub.3 +3 EtOH→Cl(CH.sub.2).sub.3 Si(OEt).sub.3 +3 MeOH
This reaction is preferably run by continuously feeding ethanol while removing by-product methanol from the system to drive the equilibrium toward chloropropyltriethoxysilane. The reaction can conveniently begin at atmospheric pressure and reflux temperatures, i.e., a pot temperature of from about 80° to about 100° C. At the end of the reaction, the excess ethanol can be stripped off using vacuum and a somewhat higher temperature. A typical final condition for the ethanol strip would be a temperature of about 120° C. and a pressure of about 100 mm Hg.
The active metal sulfide solution, e.g., product of the H 2 S-active metal alkoxide reaction described above, is added to a slurry of elemental sulfur in the halohydrocarbylalkoxysilane. After the hydrogen sulfide addition and reaction is completed, the reaction mixture is cooled, e.g., to about 25° C., and the solution to is added to a slurry of S/Cl(CH 2 ) 3 Si(OEt) 3 at around 40° to 45° C., until addition is complete, at a rate commensurate with the heat removal capability of the reactor. In laboratory glassware, this may require from about 1 to 3 hours. When the addition is complete, the reactor is preferably heated to about 80° C. and held at reflux for a suitable time, i.e., from about 1 to 3 hours, typically about 1.5 hours. It is preferred to maintain agitation in the reactor to insure solubilization and reaction, and to maintain in suspension the salt particles formed during the reaction. During this period, the system is preferably maintained at atmospheric pressure under a nitrogen blanket, to keep air out of the kettle to avoid oxidation which may contribute to a darkening of product color. After this reflux period, the reactor is immediately cooled, i.e., to about 25° C.
For the preferred product, the desired reaction is:
Na.sub.2 S+3 S+2 Cl(CH.sub.2).sub.3 Si(OEt).sub.3 →(EtO).sub.3 Si(CH.sub.2).sub.3 S.sub.4 --(CH.sub.2).sub.3 Si(OEt).sub.3
Salt Removal
The reaction produces the desired product and also produces salt. In the preferred reaction, sodium chloride salt produced in the sulfur and chloropropyl-triethoxysilane addition step can be removed by filtering or centrifuging. If filtration is used, the media pore size should be about 5μ. Typically, no filter aid is necessary since the average particle size is fairly large, but one can be employed if needed. If centrifuging is employed, a basket or continuous scroll-type device can be employed.
The resulting filtercake will contain residual liquid product and can be washed, e.g., with ethanol to improve overall product yield.
Solvent Strip
The process preferably includes a step of stripping off detrimental levels of solvent, preferably reducing the solvent concentration to less than about 5% by weight. In the preferred process as described above, assuming an ethanol wash has not been used, the crude product contains about 60 wt % ethanol. Stripping, preferably in a single stage, can be employed to yield a product containing less than about 2 wt % ethanol. One suitable stripping technique is batch stripping of the crude material in a reactor, e.g., to a final condition of 100° C. and 50 mm Hg absolute pressure. A small quantity of salt may precipitate out during the ethanol strip, and it is preferred to subject the product to a final filtration as necessary to remove this.
EXAMPLES
The following examples are presented for the purpose of further illustrating and explaining the invention, and are not to be taken as limiting in any regard. Unless otherwise indicated, all parts and percentages are based on the weight of the components at the indicated stage of processing.
Example 1
This example describes the preparation of the preferred end product, 3,3'- bis (triethoxysilylpropyl) tetrasulfide. To accomplish this result, sodium ethoxide was prepared fresh.
Preparation of Sodium Ethoxide
To a 500 ml glass reactor equipped with a feed funnel, a reflux column, a fritted glass sparge tube and thermometer, 17.0 grams of dry sodium chunks were added. Then, the reactor and the column were purged with N 2 for >5 minutes. Then, 227.4 grams of ethanol were charged into the feed funnel. During this step, the ethanol was added slowly enough to prevent the sodium from melting. After 85 minutes, all of the sodium was dissolved and the reactor was cooled from about 80° C. to about 40° C. for the next step.
H 2 S Reaction with Sodium Ethoxide
Addition of hydrogen sulfide gas was started through a fritted glass sparge tube. The reaction was run with vigorous agitation during sparge. During a feed time of just under an hour, 12.7 grams of hydrogen sulfide gas was fed to the reactor. The solution was added to an addition funnel for later use.
Preparation of Chloropropyltriethoxysilane
Chloropropyltrimethoxysilane was separately transesterified to the ethyl ester, chloropropyltriethoxysilane, in a 1 liter glass reactor equipped with a heating mantle, thermometer, ethanol addition funnel and a 5 tray, 1 inch diameter glass Oldershaw column. This column should have at least about 3 theoretical trays.
The reactor was initially charged with 527.15 grams of chloropropyltrimethoxysilane, 1.05 grams of p-toluenesulfonic acid (2000ppm), and 130 grams of ethanol. During the first part of the reaction the reactor temperature was run in the range 80°-90° C. Then the ethanol feed rate was cut back and the reactor was run at 98°-115° C., to help drive MeOH out of the reactor. A reflux ratio of about 8:1 was used for the entire run. The ethanol usage was 2.3 times the theoretical amount. The reaction was run for about 8.9 hours, over a two day period. High temperature (111° C.) at the end of the run helped assure a relatively low residual ethanol concentration, i.e., 6.7%. This material could be vacuum stripped to reduce the ethanol further.
______________________________________PRODUCT ANALYSIS BY GAS CHROMATOGRAPHY______________________________________Ethanol 6.7 area %Chloropropylmethoxydiethoxysilane 1.02 area %Chloropropyltriethoxysilane 90.7 area %______________________________________
Reaction of Na 2 S Solution with Sulfur/Chloropropyltriethoxysilane
The chloropropyltriethoxysilane made from transesterification of the corresponding methyl ester was used as the raw material to make 3,3'-bis (trialkoxysilylpropyl) tetrasulfide.
To a second glass reactor were added 184.6 grams chloropropyltriethoxysilane and 36.0 grams of ground sulfur. The reactor was equipped with a heating mantle, reflux column, agitator and thermometer. The silane-sulfur slurry was heated to 45° C. Then the Na 2 S solution (contained in the addition funnel) was continuously added over a 2.3 hour period, during which the reaction temperature was maintained between 39° C. and 49° C. After the Na 2 S addition was completed, the reaction was held at 45° C. for 1 hour, and then held at 75° C. for 1.5 hours.
Recovery of Product
The reactor was then cooled to room temperature. Its contents were filtered to remove NaCl solids formed in the reaction. Next the filtrate from the above step was stripped to 100° C. and 50 mm Hg to remove ethanol. Finally the stripped product was filtered through a 0.25 micron filter.
The final product had a weight of 190.6 grams. It was analyzed by gas chromatography (GC) and for % sulfur and shown to contain about 70% 3,3'-bis(triethoxysilylpropyl)tetrasulfide and about 25% 3,3'-bis(triethoxysilylpropyl) trisulfide at 22.4% contained sulfur. Less than 1% chloropropyltriethoxysilane was present. The gas chromatographic analysis was virtually identical to commercially available product and that produced by the process disclosed in U.S. application Ser. No. 08/314,204 cited above.
Example 2
Reaction of Na 2 S/Chloropropyltriethoxysilane Product with Sulfur
This example illustrates the surprising results applicants achieve using the process of their invention as well as the importance of the ordered addition of reactants in applicants' claimed process.
In equipment analogous to that used above, a solution of Na 2 S in ethanol was prepared as above from 260.7 grams of 21% sodium ethoxide in ethanol and 12.6 grams of H 2 S gas. The solution was heated to reflux and 182.4 grams of chloropropyltriethoxysilane were added over a 1 hour period. After cooling to 25° C., 35.6 grams of sulfur were added, and heat applied to reflux within 30 minutes, followed by heating at reflux for 90 minutes. After filtration, gas chromatographic analysis of the unstripped product showed the major non-solvent component to be monosulfide, (EtO) 3 Si(CH 2 ) 3 S--(CH 2 ) 3 Si(OEt) 3 , with significant unreacted chloropropyltriethoxysilane. The unfiltered reaction mixture contained unreacted sulfur as well as the expected salt.
The above description is for the purpose of teaching the person of ordinary skill in the art how to practice the present invention and it is not intended to detail all of those obvious modifications and variations of it which will become apparent to the skilled worker upon reading the description. It is intended, however, that all such obvious modifications and variations be included within the scope of the present invention which is defined by the following claims. The claims cover the indicated components and steps in all arrangements and sequences which are effective to meet the objectives intended for the invention, unless the context specifically indicates the contrary. | Sulfur-containing organosilicon compounds useful as coupling agents in vulcanizable rubbers to enhance various properties, including low rolling resistance for automobile tires, are prepared. Preferred compounds include Ω,Ω'-bis (trialkoxysilylalkyl) polysulfides. The compounds are prepared by reacting sodium ethoxylate with hydrogen sulfide gas to yield a sodium sulfide solution, and then reacting this product with a slurried mixture of elemental sulfur and chloropropyltriethoxysilane to form the compound 3,3'-bis (triethoxysilylpropyl) tetrasulfide. The use of hydrogen sulfide gas and sodium metal alcoholates provides an efficient and economical process. | 2 |
FIELD OF THE INVENTION
The invention relates to semiconductor structures and, more particularly, to chamferless via structures and methods of manufacture.
BACKGROUND
Integrated circuit(s) typically include a plurality of semiconductor devices and interconnect wiring. Networks of metal interconnect wiring typically connect the semiconductor devices from a semiconductor portion of a semiconductor substrate. Multiple levels of metal interconnect wiring above the semiconductor portion of the semiconductor substrate are connected together to form a back-end-of-the line (BEOL) interconnect structure.
Several developments have contributed to increased performance of contemporary ICs. One such development is technology scaling which results in higher integration of structures, e.g., transistors, wiring, etc. However, technology scaling has posed several challenges including, e.g., process variation, stricter design rules, etc. For example, in trench first via last metal hardmask integration schemes, excessive non-self-aligned via (Non-SAV) chamfering can result during trench formation. This integration scheme results in chamfering which is very difficult to control, and can result in poor yields, jagged surfaces and shorting issues.
SUMMARY
In an aspect of the invention, a method comprises: forming at least one self-aligned via within at least dielectric material; plugging the at least one self-aligned via with material; forming a protective sacrificial mask over the material which plugs the at least one self-aligned via, after a recessing process; forming at least one trench within the dielectric material, with the protective sacrificial mask protecting the material during the trench formation; removing the protective sacrificial mask and the material within the at least one self-aligned via to form a wiring via; and filling the wiring via and the at least one trench with conductive material.
In an aspect of the invention, a method comprises: forming at least one self-aligned via within an optical planar layer and ultra low-k dielectric material; plugging the at least one self-aligned via with material selective to the ultra low-k dielectric material; recessing the material; removing the optical planar layer and underlying etch stop material to expose the ultra low-k dielectric material, wherein the removing step further recesses the material to below spacers formed above the ultra low-k dielectric material; forming a protective sacrificial mask over the material which plugs the at least one self-aligned via; forming at least one trench within the dielectric material, with the protective sacrificial mask protecting the material during the forming of the at least one trench; removing the protective sacrificial mask and the material within the at least one self-aligned via to form a wiring via; and filling the wiring via and the at least one trench with conductive material.
In an aspect of the invention, a structure comprises a conductive line and via formed in a low-k dielectric material wherein the via is chamferless and the low-k dielectric material is continuous with no etch stop layer at a line/via junction.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention is described in the detailed description which follows, in reference to the noted plurality of drawings by way of non-limiting examples of exemplary embodiments of the present invention.
Prior to discussing the particulars of each of the figures, it is to be noted that each set of figures include a cross sectional view of a structure along a self-aligned via (SAV) direction, e.g., FIGS. 1A, 2A, 3A, 4A, 5A, 6A, 7A, 8A, 9A and 10A , and a set of figures including a cross sectional view of a structure along a non-self-aligned via (non-SAV) direction, e.g., FIGS. 1B, 2B, 3B, 4B, 5B, 6B, 7B, 8B, 9B and 10B .
FIG. 1A shows a cross sectional view of a beginning structure and respective fabrication processes along a self-aligned via (SAV) direction; whereas, FIG. 1B shows a cross sectional view of the structure of FIG. 1A along a non-SAV direction, in accordance with aspects of the invention.
FIGS. 2A and 2B show structures with openings and respective fabrication processes in accordance with aspects of the invention.
FIGS. 3A and 3B show structures with via fill material within the openings and respective fabrication processes in accordance with aspects of the invention.
FIGS. 4A and 4B show the via fill material recessed within the openings and respective fabrication processes in accordance with aspects of the invention.
FIGS. 5A and 5B show additional structures within the fabrication processes, and respective fabrication processes in accordance with aspects of the invention.
FIGS. 6A and 6B show additional structures within the fabrication processes, and respective fabrication processes in accordance with aspects of the invention.
FIGS. 7A and 7B shows a protective sacrificial mask on exposed portions of the via fill material amongst other structures, and respective fabrication processes in accordance with aspects of the invention.
FIGS. 8A and 8B show a plurality of trenches within dielectric material, and respective fabrication processes in accordance with aspects of the invention.
FIGS. 9A and 9B show chamferless wiring vias, and respective fabrication processes in accordance with aspects of the invention.
FIGS. 10A and 10B show metal fill material within the chamferless wiring vias (wiring lines), and respective fabrication processes in accordance with aspects of the invention.
DETAILED DESCRIPTION
The invention relates to semiconductor structures and, more particularly, to chamferless via structures and methods of manufacture. In embodiments, the present invention implements a protective sacrificial mask, e.g., Ruthinium, in order to protect a via structure during back end of the line (BEOL) processing. In embodiments, the Ruthinium or other protective sacrificial mask material described herein will protect gap fill material and underlying materials, e.g., Titanium Nitride (TiN) hardmask, during trench interlevel dielectric (ILD) reactive ion etching (RIE) processes. The protection provided by the protective sacrificial mask will reduce via CD (critical dimension) increase and improve non-SAV (self-aligned via) angle and chamfer roughness caused by ILD damage caused during the trench ILD RIE process. In this way, the processes of the present invention can be used to form a chamferless via structure.
In embodiments, the fabrication processes include making a chamferless via structure of a dual damascene line/via formed in an ultra-low k dielectric material. In more specific embodiments, the fabrication processes include, amongst other steps, using a gap fill material (e.g., SiARC) in a via opening etched in a low-k dielectric material, while trench openings are subsequently formed in the low-k dielectric material. In embodiments, the gap fill material can be protected with selectively formed Ruthenium, which is used as a mask during trench opening formation processes. Advantageously, the processes described herein will result in final wiring structures comprising a dual damascene line and via formed in a low-k dielectric wherein the via is chamferless and the low-k dielectric material is continuous (e.g., there is no intermediate etch stop layer at the dual damascene line/via junction).
The chamferless via structures of the present invention can be manufactured in a number of ways using a number of different tools. In general, though, the methodologies and tools are used to form structures with dimensions in the micrometer and nanometer scale. The methodologies, i.e., technologies, employed to manufacture the chamferless via structures of the present invention have been adopted from integrated circuit (IC) technology. For example, the structures of the present invention are built on wafers and are realized in films of material patterned by photolithographic processes on the top of a wafer. In particular, the fabrication of the chamferless via structures of the present invention uses three basic building blocks: (i) deposition of thin films of material on a substrate, (ii) applying a patterned mask on top of the films by photolithographic imaging, and (iii) etching the films selectively to the mask.
Now referring to the figures, as shown in FIGS. 1A and 1B , the structure 10 includes a metal layer 12 , e.g., copper or tungsten, amongst other metal or metal alloys. A block material 14 such as an NBLOK is formed on the metal layer 12 . In embodiments, the block material 14 can be about 20 nm in depth, although other dimensions are contemplated by the present invention. A dielectric material 16 is formed on the block material 14 . In embodiments, the dielectric material 16 is an ultra low-k dielectric material known to those of ordinary skill in the art. The dielectric material 16 can be formed to a thickness of about 100 nm; although other dimensions are also contemplated by the present invention.
Still referring to FIGS. 1A and 1B , a thin film of etch stop layer or hardmask material 18 , e.g., alloy material, is deposited on the dielectric material 16 . In embodiments, the thin film of etch stop layer or hardmask material 18 can be SiNH deposited to a thickness of about 10 nm; although other dimensions are also contemplated by the present invention. Another hardmask 20 , e.g., TiN, is deposited on the thin film of etch stop layer or hardmask material 18 , followed by the formation of spacers 22 , e.g., nitride material. The hardmask 20 and spacers 22 can be formed using conventional deposition processes, e.g., CVD, followed by lithography and etching, e.g., RIE, processes known to those of ordinary skill in the art such that further description is not required for an understanding of the invention. The lithography and etching process will result in a self-aligned via structure as described herein.
Still referring to FIGS. 1A and 1B , an optical planarization layer (OPL) 24 can be deposited over the structure, e.g., hardmask 20 and spacers 22 and exposed portions of the thin film of etch stop layer or hardmask 18 . In embodiments, the OPL 24 can be spun on and baked, or can be deposited by CVD. OPL can be baked at lower temperatures, such as 150-200° C. to avoid damaging any other materials. A hardmask 26 is deposited on the OPL 24 . In embodiments, the hardmask 26 is a low temperature oxide deposited to a thickness of about 30 nm; although other dimensions are also contemplated by the present invention.
The hardmask 26 is patterned to form openings 28 . In embodiments, the openings 28 are formed by conventional lithography and etching processes. For example, a resist is formed over the hardmask 26 , which is exposed to energy (light) to form a pattern (openings). A reactive ion etching (RIE) process is then performed through the openings of the resist to form the openings 28 in the hardmask 26 . The resist is then removed using conventional stripants or oxygen ashing processes.
As shown in FIGS. 2A and 2B , openings 30 (e.g., self-aligned via structures 30 ), are formed in the materials to the underlying metal layer 12 . As shown in FIG. 2A , the self-aligned via structures 30 extend between the spacers 22 and the hardmask 20 , and expose the underlying metal layer 12 . The self-aligned via structures 30 can be formed through several selective etch chemistries, selective for each of the materials. The different chemistries will be selective to different materials as should be known to those of ordinary skill in the art such that further description is not required for an understanding of the invention.
In embodiments, the different etching steps can be provided within the same etch chamber, as an example. For example, a first etch chemistry is used to remove portions of the OPL 24 . A second etch chemistry is then used to remove the etch stop layer 18 . with subsequent etch chemistries used to remove the dielectric layer 16 and hardmask layer 14 , respectively. In this way, the underlying metal layer 12 can be exposed.
In embodiments, the self-aligned via structures 30 can undergo a wet etching process to remove any residual RIE residue to improve fill adhesion. In embodiments, the self-aligned via structures 30 can have an aspect ratio of, e.g., about 15:1. For example, in embodiments, the dimensions of the self-aligned via structures 30 in the SAV direction can be about 20 nm, whereas, the dimensions of the self-aligned via structures 30 in the non-SAV direction can be about 30 nm.
In FIGS. 3A and 3B , a via fill material 32 is deposited within the self-aligned via structures 30 . During this deposition process, residual via fill material 32 may form on the surface of the OPL 24 . In embodiments, the via fill material 32 can be SiARC (e.g., antireflective coating of Si). In alternate embodiments, the via fill material 32 can be an OPL. In still additional alternate embodiments, the via fill material 32 can be a spin on material, e.g., spin on glass. In still additional alternate embodiments, the via fill material 32 can be an oxide such as an ultra porous material, e.g., ultra low-k dielectric material such as SiCOH.
In embodiments, the via fill material 32 should have a viscosity that allows complete fill of the self-aligned via structures 30 . In alternate embodiments, the via fill material 32 may not completely fill the self-aligned via structures 30 . For example, air gaps can be provided below the etch stop layer 18 , e.g., at the dielectric layer 16 . In embodiments, the via fill material 32 does not need to be planarized or conform to photolithography specifications.
In FIGS. 4A and 4B , the via fill material 32 is etched slightly to form recesses 34 within the OPL 24 . In embodiments, the recesses 34 can be tuned to specific dimensions based on etch rates and chemistries. Following the recess of the via fill material 32 , the OPL material and additional portions of the via fill material 32 are removed as shown in FIGS. 5A and 5B . These materials can be removed by selective etching chemistries as described herein.
In FIGS. 6A and 6B , any exposed etch stop layer material 18 can be removed using a selective etch chemistry. This selective etch chemistry can also remove portions of the via fill material 32 to below the spacers 22 . In embodiments, the removal of the etch stop layer material 18 will allow the formation of a trench structure in subsequent fabrication processes.
In FIGS. 7A and 7B , a protective sacrificial mask 34 is formed on the exposed portions of the via fill material 32 . The protective sacrificial mask 34 can also be formed on exposed portions of the etch stop layer 18 and hardmask 20 . In embodiments, the protective sacrificial mask 34 is a selective deposition material, which does not deposit or adhere to oxide, e.g., dielectric material 16 . In this way, the dielectric material 16 remains exposed for future trench formation processing.
By way of example and as discovered by the inventors, the protective sacrificial mask 34 can be Ruthinium. Advantageously, Ruthinium does not adhere to oxide, e.g., dielectric material 16 , but will adhere to organics and metals. Also, Ruthinium has been found to be resistant to etch chemistries used for trench formation processes. In embodiments, the protective sacrificial mask 34 can be formed by an atomic layer deposition (ALD) process, controllable to 1 nm.
As shown in FIGS. 8A and 8B , the exposed dielectric material 16 undergoes etching processes to form a trench 36 . In embodiments, the protective sacrificial mask 34 will protect the underlying materials and, more specifically, the self-aligned via structures 30 . In this way, the self-aligned via structures 30 will not become damaged during processing of the trenches 36 . The trenches 36 can have a depth of about 60 nm to about 80 nm; although other dimensions are also contemplated by the present invention.
As shown in FIGS. 9A and 9B , the protective sacrificial mask 34 , the etch stop layer 18 and hardmask 20 can be removed, followed by removal of the via fill material 32 . In embodiments, the via fill material 32 will protect the underlying metal layer 12 during the removal of the protective sacrificial mask 34 , etch stop layer 18 and hardmask 20 , allowing for aggressive removal of the etch stop layer 18 and hardmask 20 . In embodiments, the protective sacrificial mask 34 , etch stop layer 18 and hardmask 20 can be removed using a wet etch process. Moreover, in embodiments, the via fill material 32 can be removed by a dry or wet etch removal process. In embodiments, the via fill material 32 can also be removed with the removal of the etch stop layer 18 and/or hardmask 20 . In any scenario, the removal of the via fill material 32 will form a wiring via 38 with vertical sidewalls, e.g., chamferless sidewalls. By way of example, the sidewall angle would be greater than 85°, and preferably has a constant angle in the dielectric material 16 . In this way, the wiring via 38 would be chamferless.
As shown in FIGS. 10A and 10B , metal fill material 38 is formed within the wiring via 38 and the trench 36 . The metal fill material 38 can be a copper material formed by an electroplating process as is well known to those of skill in the art. In embodiments, prior to the metal fill process, any residual RIE material can be cleaned from the wiring via 38 and the trenches 36 using a wet etch process, followed by deposition of a barrier and seed layer. The barrier layer can prevent metal diffusion into the ultra-low-k dielectric and it can promote seed layer adhesion. After the deposition of a barrier and seed layer, the electroplating process can commence to form metal lines, e.g., metal fill material 38 . Any residual metal fill material 38 on a surface of the structure can be removed by a conventional planarization process. e.g., chemical mechanical polishing (CMP).
The method(s) as described above is used in the fabrication of integrated circuit chips. The resulting integrated circuit chips can be distributed by the fabricator in raw wafer form (that is, as a single wafer that has multiple unpackaged chips), as a bare die, or in a packaged form. In the latter case the chip is mounted in a single chip package (such as a plastic carrier, with leads that are affixed to a motherboard or other higher level carrier) or in a multichip package (such as a ceramic carrier that has either or both surface interconnections or buried interconnections). In any case the chip is then integrated with other chips, discrete circuit elements, and/or other signal processing devices as part of either (a) an intermediate product, such as a motherboard, or (b) an end product. The end product can be any product that includes integrated circuit chips, ranging from toys and other low-end applications to advanced computer products having a display, a keyboard or other input device, and a central processor.
The descriptions of the various embodiments of the present invention have been presented for purposes of illustration, but are not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein was chosen to best explain the principles of the embodiments, the practical application or technical improvement over technologies found in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein. | Chamferless via structures and methods of manufacture are provided. The method includes: forming at least one self-aligned via within at least dielectric material; plugging the at least one self-aligned via with material; forming a protective sacrificial mask over the material which plugs the at least one self-aligned via, after a recessing process; forming at least one trench within the dielectric material, with the protective sacrificial mask protecting the material during the trench formation; removing the protective sacrificial mask and the material within the at least one self-aligned via to form a wiring via; and filling the wiring via and the at least one trench with conductive material. | 7 |
This case is filed under 35 USC 371 as the U.S. atage of PCT/EP95/02780 filed Jul. 14, 1995.
AREA OF THE INVENTION
The present invention relates to 7-O-carbamoylheptose derivatives, to a process for their production and to their use for the production of reagents and compositions for the diagnosis and therapy of pseudomonas infections in humans and animals, and to a screening process for their determination in Gram-negative bacteria.
BACKGROUND OF THE INVENTION
Bacteria of the Pseudomonadaceae family are Gram-negative organisms which occur ubiquitously and whose pathogenicity for humans is normally very weakly developed. P. aeruginosa, by contrast, is a human-pathogenic species and occurs frequently in wound infections and there especially as secondary infection in cases of higher-degree burns of the skin, and in cases of suppurative otitis media. In immunocompromised patients and in cases of cystic fibrosis it is particularly the antibiotic-resistant pseudomonads which are of outstanding medical importance McManus et al., J. Trauma 21 (1981) 753-763. Bodey et al., Rev. Inf. Dis., 5 (1983), 279-313, Winkler et al., Klin. Wochenschrift, 63 (1985) 490-498!.
In terms of taxonomy, pseudomonads comprise a very heterogeneous family. Their species-related heterogeneity represents a considerable impediment to the medical diagnosis and therapy of pseudomonas infections. This is why it was only recently proposed that this family of Pseudomonadaceae be divided into five different subgroups N. J. Palleroni, Antonie Van Leeuwenhoek, 64 (1993) 231-251!. The first group (RNA group 1) includes P. aeruginosa, P. fluorescens and P. putida. The second group (RNA group 2) comprises the pseudomonads which are pathogenic for plants and animals (for example P. plantarii) and is now referred to as burkholderia. Finally, a distinction is also made between comamonas (group 3) and the purple bacteria (group 4) which continue to be referred to as "pseudomonas" (for example P. diminuta, P. vesicularis) and lastly also xanthomonas (RNA group 5).
Beyond this, pseudomonads are also of biomedical interest for other reasons. They are extremely resistant to antibiotics A. M. Kropinski et al., Antimicrob. Agents Chemother., 36 (1985) 58-73!. There is evidence that this antibiotic resistance is associated with the structure of the cell wall membrane, that is to say with a high density of negatively charged phosphate groups on molecules in the outer cell wall membranes R. E. W. Hancock et al., in: Bacterial Cell Wall, J. M. Ghuysen and R. Hakenbeck (eds.), Elsevier Amsterdam, 1994, 263-279). Such surface structures are in all Gram-negative bacteria essentially integral proteins of the cell membrane (OMP, porins) and the lipopolysaccharide (LPS, endotoxin). These molecules represent antigens which show high genus-, species- and subspecies-specific immunogenicity and, during the course of an infection, induce serotype-specific antibodies which may be of great importance to both diagnosis and therapy.
Over the course of the last decade it has been possible to acquire considerable knowledge about the serological and biological properties of these antigens. There has also been intensive study and elucidation of the LPS structures and there particularly of their immunogenic outer components (O chains) of the 17 serotypes now known. There has been complete chemical analysis of all P. aeruginosa O chains, and some of them have also been synthesized and classified serologically into various immunotypes (Fischer) and serotypes (Lanyi, Habs) N. K. Kochetkov and Yu. A. Knirel, Sov. Sci. Rev. B. Chem. 13 (1989) 1-101!. Based on this structural knowledge, various P. aeruginosa serotyping kits with monoclonal antibodies have been produced and are still commercially available. The disadvantage of these antibody test cocktails is that they detect only the known antibodies, but all monoclonal O-specific antibodies are necessary in order to detect all O types.
Besides the antigenic assay processes which have been known for a long time for the immunologically highly specific O chains, there has recently been development of cross-reacting monoclonal antibodies whose epitope is located not in the highly variable O chain of the lipopolysaccharide but in the less variable core oligosaccharide. Since these structures make essential contributions to the function of the outer cell membrane, core oligosaccharides are regarded rather as conservative structural elements of the immunogenic LPS, against which it might be possible to produce broadly cross-protecting antibodies. This has recently been experimentally demonstrated for the first time. A mouse monoclonal antibody (MAb) whose specificity was directed against the core region showed broad cross-reactivity and broad cross-protection for all five Escherichia coli (R1, R2, R3, R4, K-12) and for the Salmonella minnesota core oligosaccharide structure, irrespective of the structure of the O chain of the particular LPS Di Padova et al., Infect. Immun. 61 (1993) 3863-3872!. This MAb (WN1 222-5) of the IgG2a class confers broad cross-protection against S. minnesota and E. coli endotoxin but not against P. aeruginosa or Klebsiella pneumoniae. The reason for this is ascribed to the different core oligosaccharide structure. The core oligosaccharide structures of P. aeruginosa and K. pneumoniae have hitherto been analysed only incompletely or are substantially unknown.
In a study in which various rough form mutants of P. aeruginosa were produced and their core oligosaccharide was chemically investigated P. S. N. Rowe & P. M. Meadow, Eur. J. Biochem. 132 (1983) 329-337!, the first proposed structures of the core region were published. One structural pecularity was the presence of the amino acid alanine (Ala) in the outer core oligosaccharide of all the P. aeruginosa rough form mutants investigated. This proposed structure was not revised and improved until ten years later, on a P. aeruginosa mutant R5 (Habs 06)! by 1 H-NMR spectroscopy E. Altman et al., Int. Carb. Conference, Paris 1992, E. Altman et al., 2nd IES Conference, Vienna 1992!.
However, very recent investigations in our laboratory have revealed that even this structure of the core oligosaccharide of the deep rough mutants R5 (Habs 06(! derived from the rough form mutants PAClR of P. aeruginosa is still incomplete. It was initially known that this core region is extensively phosphorylated. On the other hand, the degradation methods and analytical processes used by E. Altman et al. were essentially unsuitable to allow the 7-O-carbamoyl-L-glycero-D-manno-heptopyranose which is described in detail for the first time according to the present invention to be identified and analyzed by spectrometry ( 1 H-NMR).
SUMMARY OF THE INVENTION
The inventors have investigated the chemical structure of the lipopolysaccharide of pseudomonads with the aim of providing specific mono- and disaccharides which can be employed as serological markers in the diagnosis and therapy of pseudomonas infections.
In these investigations it was possible to analyze and completely characterize the chemical structure of a previously unknown 7-O-carbamoyl-L-glycero-D-manno-heptopyranose in the core oligosaccharide of the LPS of pseudomonads of RNA group 1. It has not been possible to find this heptopyranose in other Gram-negative bacteria apart from pseudomonads of RNA group 1 (for example in all Enterobacteriaceae).
The invention therefore relates to 7-O-carbamoylheptose derivatives of the general formula (I) ##STR2## in which R is the substituent R 1 or a group of the general formula (II) ##STR3## in which R 1 is a hydrogen atom, a methyl group or a linker substituent suitable for a covalent coupling.
The invention furthermore relates to a process for the production of the 7-O-carbamoylheptose derivatives which is characterized in that a lipopolysaccharide of pseudomonads of RNA group 1 is created with hydrofluoric acid, the resulting product is dialysed against water until a neutral pH is reached, the lipopolysaccharide which has been dephosphorylated in this way is methanolyzed, and subsequently a permethylation or peracetylation is carried out, the resulting 7-O-carbamoylheptose derivatives are fractionated by liquid chromatography (checking the purity by gas-liquid chromatography or combined gas-liquid chromatography/mass spectrometry) and, if required, the substituent R 1 is introduced into the resulting 7-O-carbamoylheptose derivatives by a process known per se.
The invention furthermore relates to a screening process for determining the 7-O-carbamoylheptose derivatives in Gram-negative bacteria, which is characterized in that intact bacteria are treated, without previous removal of the lipopolysaccharide, with hydrofluoric acid, then hydrolyzed or methanolyzed to liberate the heptose derivatives, and subsequently a permethylation is carried out and the permethylated product is analyzed by gas-liquid chromatography or combined gas-liquid chromatography/mass spectrometry.
The 7-O-carbamoylheptose derivatives of the general formula (I) can be used to produce reagents and compositions for the diagnosis and therapy of pseudomonas infections in humans and animals.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The linker substituent indicated by R 1 in the general formula (II) is preferably a cysteamine residue, an allyl group or a straight-chain or branched-chain C 1-18 -alkyl group which may contain a terminal hydroxyl, amino, acyl, carboxyl or allyl group. R 1 is preferably a hydrogen atom or a methyl group.
The present invention has succeeded in making the heptose region in the core oligosaccharide of the LPS of pseudomonads of biomedical importance available for analysis and in complete characterization of the phosphate-free structure thereof. Furthermore, the invention has succeeded in making it possible to isolate this previously unknown sugar from these bacteria and to analyze and quantify it by combined gas chromatography/mass spectrometry (GC-MS).
It has been possible to date to identify the novel 7-O-carbamoylheptopyranose only in pseudomonads of RNA group 1 (especially in the human-pathogenic P. aeruginosa and in P. fluorescens).
Furthermore, the novel sugar occurs in the LPS of all immunotypes of P. aeruoginosa (Fischer 2,7), investigated to date, irrespective of the structure of the O chain. No exceptions to this rule are known as yet. The 7-O-carbamoylheptopyranose does not occur in the LPS of pseudomonads which are pathogenic to plants (for example P. plantarii), which are now assigned to burkholderia, no longer to the group of pseudomonads.
Both the diagnostic and taxonomic significance of the 7-O-carbamoylheptopyranose can be deduced from these findings. The 7-O-carbamoylheptopyranose is likewise absent from all other Gram-negative bacteria investigated to date: Klebsiella pneumoniae, K25; Yersinia enterocolitica, mutant 490 M; Campylobacter jejuni RN 16 0:58; CCUG 10936; Proteus mirabilis, mutant R 45 ; Haemophilus influenzae, B, strain Eagan, Vibrio parahaemolyticus, serotype 012, Salmonella minnesota, SF 1111, and E. coli O111 were negative for the 7-O-carbamoylheptose in the screening process, which underlines once again the diagnostic importance of this newly discovered sugar.
Using the sugar according to the invention it has now become possible further to improve the species-specific diagnosis of pseudomonads and their taxonomic classification.
Since it is known that monoclonal antibodies directed against epitopes of the inner and outer core regions are able also to recognize wild-type LPS with analogous core oligosaccharides Di Padova, F. et al., Infect. Immun., 61 (1993) 3863-3872 and Rietschel, e.Th. et al., FASEB. J., 8 (1994) 217-225!, it is possible on the basis of the present structure elucidation to define species-specific epitopes by means of monoclonal antibodies which cruccially simplify and improve the serodiagnosis of these human-pathogenic organisms. This serodiagnosis can at present be carried out only via the O-specific chain, with the known disadvantages of lacking cross-specificities.
The pseudomonads employed in the process according to the invention, which occur in soil, water, waste water, on plants and in foodstuffs, are extremely well-known microorganisms which can also be obtained from recognized depositary authorities.
Depending on the conditions used for the methanolysis, it is possible by the process according to the invention to produce either the heptose monosaccharide or the heptose di- or oligosaccharide (see also Example 3.1 hereinafter).
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows the structural formula, the electron impact mass spectrum (1) and the Cl-- NH 3 ! mass spectrum (2) of methyl-2,3,4,6,7-penta-O-acetyl-D-glycero-α/β-D-manno-heptopyranose (compound No. 4).
FIG. 2 shows the structural formula, the electron impact mass spectrum (1) and the Cl-- NH 3 ! mass spectrum (2) of methyl-2,3,4,6,7-tetra-O-acetyl-7-O-carbamoyl-D-glycero-α/β-D-manno-heptopyranose (compound No. 5).
FIG. 3 shows the structural formula, the electron impact mass spectrum (1) and the Cl-- NH 3 ! mass spectrum (2) of methyl-7-O-(N,N-dimethylcarbamoyl)-2,3,4,6-tetra-O-methyl-D-glycero-.alpha./β-D-manno-heptopyranose (compound No. 3).
FIG. 4 shows the structural formula, the electron impact mass spectrum (1) and the Cl-- NH 3 ! mass spectrum (2) of methyl 3-O- 7-O-(N,N-dimethylcarbamoyl)-2,3,4,6-tetra-O-methyl-heptopyranosyl!-2,4,6,7-tetra-O-methyl-heptopyranoside (compound No. 12).
FIG. 5 shows the structural formula and the electron impact mass spectrum of methyl-7-O- N,N-di-(trideuteriomethyl)-carbamoyl)-2,3,4,6-tetra-O-trideuteriomethyl-D-glycero-α/β-D-manno-heptopyranose (compound No. 6).
FIG. 6 shows the structural formula, the electron impact mass spectrum (1) and the Cl-- NH 3 ! mass spectrum (2) of methyl-7-O-acetyl-2,3,4,6-tetra-O-methyl-D-glycero-α/β-D-manno-heptopyranose (compound No. 8).
FIG. 7 shows the structural formula, the electron impact mass spectrum (1) and the Cl-- NH 3 ! mass spectrum (2) of methyl 3-O-acetyl-2,3,4,6-tetra-O-methyl-heptopyranosyl!-2,4,6,7-tetra-O-methyl-heptopyranoside (compound No. 14).
FIG. 8 shows the structural formula, the electron impact mass spectrum (1) and the Cl-- NH 3 ! mass spectrum (2) of 1,5-di-O-acetyl-7-O-(N,N-dimethylcarbamoyl)-2,3,4,6-tetra-O-methyl-heptitol (compound No. 16).
FIG. 9 shows the structural formula and the electron impact mass spectrum of 1,5-tri-O-acetyl-2,3,4,6-tetra-O-methyl-heptitol (compound No. 15).
FIG. 10 shows the structural formula, the electron impact mass spectrum (1) and the Cl-- NH 3 ! mass spectrum (2) of 1,3,5-tri-O-acetyl-2,4,6,7-tetra-O-methyl-heptitol (compound No. 18).
FIG. 11 shows the structural formula and the electron impact mass spectrum of 1,3,5-tri-O-acetyl-7-O-(N,N-dimethylcarbamoyl)2,4,6-tri-O-methyl-heptitol (compound No. 17).
FIG. 12 shows the gas-liquid chromatogram (GC) of a standard of per-O-acetylated-D-glycero-D-manno-heptitol (D,D-Hep) and L-glycero-D-manno-heptitol (L,D-Hep) (top) compared with the heptitol acetates from Hep I and Hep II isolated from the core oligosaccharide of PAC605, after removal of the 7-O-carbamoyl group. Column: SPB-5™, 150° C.-3 min then 5°/min to 330° C.
FIG. 13 shows the structural formula and the 1 H-NMR spectrum of methyl-7-O-carbamoyl-LαD-Hepp-(1→3)-LαD-Hepp (1→OMe) (compound No. 9α) (360 MHZ, D 2 O, room temperature).
FIG. 14 shows the structural formula and the 13 C--NMR spectrum of methyl-7-O-carbamoyl-LαD-Hepp-(1→3LαD-Hepp-(1→OMe) (compound No. 9α). (90 MHz, D 2 O, room temperature).
FIG. 15 shows the structural formula, the molecular formula and the laser desorption mass spectrum of methyl-7-O-carbamoyl-LαD-Hepp-(1→30-LαD-Hepp-(1→OMe) (compound No. 9α).
EXAMPLE
The compounds mentioned hereinafter have the following structural formulae in which Me=methyl and Ac=acetyl. ##STR4##
______________________________________Compound No. 1:Compound No. 2: R.sup.1 = R.sup.2 = HCompound No. 3: ##STR5##Compound No. 4: R.sup.1 = R.sup.2 = AcCompound No. 5: ##STR6##Compound No. 6: ##STR7##Compound No. 7: R.sup.1 = Me, R.sup.2 = HCompound No. 8: R.sup.1 = Me, R.sup.2 = Ac ##STR8##Compound No. 9: ##STR9##Compound No. 10: R.sup.1 = R.sup.2 = HCompound No. 11: ##STR10##Compound No. 12: ##STR11##Compound No. 13: R.sup.1 = Me, R.sup.2 = HCompound No. 14: R.sup.1 = Me, R.sup.2 = Ac ##STR12##Compound No. 15: R.sup.1 = R.sup.4 = Ac, R.sup.2 = R.sup.3 = MeCompound No. 16: ##STR13##Compound No. 17: ##STR14##Compound No. 18: R.sup.1 = R.sup.3 = Ac, R.sup.2 = R.sup.4 = Me______________________________________
Materials and Methods
Cultivation of bacteria and extraction of lipopolysaccharide Pseudomonas aeruginosa bacteria (PAO, PAC605, PAC557 and R5 (Habs 06) were obtained from P. Meadow, University College, London, Great Britain Rowe, P. S. N. and Meadow, P. M., Eur. J. Biochem., 132, (1983) 329-337! and from J. S. Lam, University of Guelph, Ontario, Canada E. Altman, et al., Biochemistry 1994, submitted, E. Altman et al., Int. Carb. Conference, Paris 1992, E. Altman, et al., 2nd IES Conference Vienna 1992!. The PAO mutant is deposited at the Deutsche Sammlung von Mikroorganismen and Zellkulturen GmbH, Braunschweig, under number DSM 1707. The rough form mutant PAC 605 was cultivated in a 100 l fermenter, and the other P. aeruginosa mutants were cultivated in 2 l shake flask cultures as described Kulshin, V. A. et al., Eur. J. Biochem, 198(1991) 697-704!. Lipopolysaccharides from the strains P. aeruginosa Fischer immunotypes 2 and 7 were obtained from Prof. B. Dmitriev, Moscow, P. aeruginosa 170519, 170520 and FH-N-845 were obtained from Prof. E. S. Stanislavsky, Moscow and Pseudomonas plantarii DSM 7128 originated from the DSM Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Braunschweig and P. fluorescens ATCC 49271 was obtained from the American Type Culture Collection, Rockville, Md., USA. All other LPS cargen: Klebsiella pneumoniae, K 25; Yersinia enterocolitica, mutant 490 M; Campylobacter jejuni RN 16 0:58; CCUG 10936; Proteus mirabilis, mutant R 45 ; Haemophilus influenzae, B, strain Eagan, Vibrio parahaemolyticus; serotype O12, Salmonella minnesota, SF 1111 (S form), and E. coli O111 (S form) originated from the LPS collection of the Forschungsinstitut Borstel.
The acquired heptose was prepared as mono- or oligomer using the P. aeruginosa PAC 605 mutant. To do this, dried bacteria (38.1 g) were washed with 1 liter each of ethanol, acetone and diethyl ether, and the ethereal sediment was dried (28.6 g, 75%). The membrane fraction obtained in this way underwent enzymatic digestion with DNAse (from bovine pancreas, Boehringer, Mannheim) and RNAse (bovine pancreas, Sigma) and proteinase K (from Tritirachium album, Boehringer). Extraction took place by a modified phenol/chloroform/petroleum method PCP II (5 parts of phenol, 5 parts of chloroform, 8 parts of petroleum ether (boiling point 90°-100° C.) modified by Galanos et al., Galanos, C., Luderitz, O. and Westphal, O., J. Biochem., 9, (1969), 245-249!. Exhaustive dialysis of distilled water was then carried out. The yield was 2.2 g (6%, m/m). Extraction of all other pseudomonas strains took place in an analogous manner by the method of Galanos et al. with yields of between 1 and 5%.
Gas chromatography (GC)
The analysis by gas chromatography was carried out with a Hewlett Packard gas chromatograph (model 5890, series II), equipped with a flame ionization detector (FID). Hydrogen was used as carrier gas with a column inlet pressure of 0.08 MPa. An SPB-5™ column (30 m, 0.25 mm ID, 0.25 μm film thickness, Supelco) which was operated with a temperature gradient (150° C. for 3 min, then 5° C./min to 330° C.) served as separation column. Evaluation was carried out using Hewlett Packard Chemstation Software® on a Vectra 486/66U.
Combined gas-liquid chromatography/mass spectroscopy (GC-MS) analysis
The combined gas-liquid chromatography/mass spectroscopy (GC-MS) was carried out with a Hewlett Packard HP 5989A MS engine which was equipped with an HP 5890 series II gas chromatograph and a capillary column (HP-5®, 30 m, 0.25 mm, 0.25 μ, Hewlett Packard). Electron impact mass spectra (EI-MS) were recorded with 70 eV. Ammonia was used as reactor gas for the chemical ionization mass spectrometry (CI-MS). The spectra were evaluated with a Hewlett Packard Chemstation Software® on a Vectra 486/66U.
NMR spectroscopy
1 H-(360 MHz and 13 C-(90 MHz) NMR spectra of the mono- and disaccharides were carried out using a Bruker NMR spectrometer (model AM-360) at room temperature in D 2 O. The recording and processing of one-dimensional data and spectra with homo- ( 1 H, 1 H-COSY) and heteronuclear ( 1 H, 13 C-NMR) correlation took place using an ASPECT 3000 computer (Bruker) with the standard Bruker software DISNMIR Version 89 11 01.0.
Laser desorption mass apectrometry (LD-MS)
The laser desorption mass spectrometry (LD-MS) was carried out using a Lamma 500 instrument (Leybol-Heraeus, Cologne) in the positive mode without addition of cationizing salts as described B. Lindner et al., in: Analytical Microbiology Methods, (1990), Plenum Press New York, A. Fox, S. L. Morgan, L. Larsson and G. Odhan (eds.), pp. 149-161!.
High pressure liquid chromatography (HPLC)
The high pressure liquid chromatography (HPLC) of the methylheptopyranose mono- and dimers (2α, 9α and 10α) was carried out in a DuPont system (pump 870, gradient controller 8800) on a Zorbax NH 2 column (9×250 mm). The column was operated with a CH 3 CN--H 2 O gradient and a flow rate of 3.5 ml/min. The gradient for isolation of 9α consisted of eluent A CH 3 CN--H 2 O 925:75 (v/v)! and eluent B CH 3 CN--H 2 O 75:925 (v/v(!; 0% B-5 min-10% B-75 min-100% B-20 min-100% B!. The gradient for purification of 10α was A: 92:8, (v/v)! and B: 50:50, (v/v)!; 0% B-5 min-0% B-75 min-100% B-20 min-100% B!. Sugar components were detected in the eluate using a chiral detector (No. 1000A, Knauer) and were collected in fractions (3.5 ml) (Foxy, Colora). Aliquots of these fractions were additionally tested by thin-layer chromatography (TLC). The retention times under the specified conditions were 21 min (9α) and 40 min (2α) and 99 min (10α).
Thin-layer analysis (TLC)
The thin-layer analysis took place on silica gel 60 F 254 (Merck) aluminum plates in chloroform/methanol/water (100:100:30), v/v). The sugar derivatives were detected by spraying with 15% (v/v) H 2 SO 4 in EtOH and subsequently heating.
Derivatization and degradation reactions
1. Dephosphorylation of the LPS
LPS (20 mg) was stirred with aqueous HF (48%) at 4° C. in a Teflon vessel overnight. It was subsequently dialyzed exhaustively with water until the pH reached neutrality. The inner dialyzate was lyophilized (12.2 mg, 61% m/m).
2. Liberation of the dephosphorylated core oligosaccharide
The dephosphorylated LPS (LPS-HF) was stirred in a sodium acetate buffer solution (0.1M NaOAc, pH 4.4) at room temperature for 8 h. The dephosphorylated core oligosaccharide was isolated after removal of lipoid A by centrifugation (20,000×g, 30 min) and subsequent Sephadex G-10 chromatography (2.5×120 cm) 7.2 mg, 59%, m/m, based on LPS-HF).
3. Production and derivatization of the methyl glycosides of the heptose mono- and oligomers
3.1 Production of the heptose methyl glycosides
The dephosphorylated LPS (42 mg) was converted by treatment with HCl/MeOH into the methyl glycoside mono- and dimers. The monomers were produced by hydrolyzing in 2M HCl/MeOH at 85° C. for 30 min, and the oligomers were produced by hydrolyzing in 0.5M HCl/MeOH at 85° C. for 30 min, and were isolated by HPLC (Zorbax-NH 2 ). Yield of monomer (1, 1.4 mg) and dimer (9α, 2.2 mg)
3.2. Derivatization of the heptose methyl glycosides
3.2.1 Peracetylation
The methyl glycosides (1.5 mg) produced as in 3.1 were derivatized with acetic anhydride/pyridine (Ac 2 O/pyridine) at 37° C. for 30 min and subsequently analyzed by a GC-MS. Deuterium-labeled peracetylated heptose derivatives were produced in an analogous manner by derivatization with (CD 3 CO) 2 O/pyridine.
3.2.2. Permethylation
The heptoses and the dephosphorylated core oligosaccharide (2 mg of each) were methylated by the method of Ciucanu and Kerek Ciucanu, C. and Kerek, F., Carbohydr. Res., 131 (1984) 209-217!. The permethylated heptose derivatives or oligosaccharides were purified on a silica gel column (silica gel 60, 70-230 mesh, 0.5×5 cm). To do this, the columns were equilibrated with chloroform and eluted with an increasing concentration of methanol (M) in chloroform (C) (C-M 95:5; v/v). Trideuterio-labeled permethylated heptose derivatives were produced in an analogous manner by derivatizing with trideuterioiodomethane (CD 3 I) in place of iodomethane. The heptose was perethylated using ethyl iodide in place of iodomethane.
3.2.3 Reductive cleavage of the dimethylcarbamoyl radical using lithium aluminum hydride
Systematic preliminary investigations on the permethylated 7-O-carbamoylheptose revealed that the 7-O-carbamoyl substituent is retained as N,N-dimethyl-7-O-carbamoyl radical on the heptose after dephosphorylation (48% HF), NaOAC hydrolysis, methanolysis and permethylation. To liberate 7-O-carbamoylheptose, 2 mg of each of the permethylated N,N-dimethyl-7-O-carbamoylheptose monomer 3 or dimer 12 were dissolved in dry diethyl ether (1 ml) and stirred with 7.5 mg of lithium aluminum hydride (LiAlH 4 ) at room temperature for 30 min. The solvent was blown off in a stream of nitrogen, and excess LiAlH 4 was decomposed by dropwise addition of water. For further purification, the product was taken up in chloroform/methanol (98:2 , v/v) and, after removal of the excess salt by centrifugation, was dried (yields: 7, 0.9 mg and 13, 0.7 mg).
3.2.4. Regioselective resubstitution of the decarbamoylated heptose mono- and dimer
The heptose derivatives 7 and 13 were heated with N,N-dimethylcarbamoyl chloride (50 μl, SIGMA) in pyridine (500 μl) at 85° C. for 4 h. Subsequently, the solvent and reagent were removed under oil pump vacuum and the product was investigated by mass spectrometry. As an alternative to the resubstitution using N,N-dimethylcarbamoyl chloride, derivatization was carred out with acetic anhydride/pyridine (3.2.1.) and the resulting products (8 and 14) were investigated by GLC-MS.
3.2.5. Methylation analysis of the heptose to determine the binding ratios in the heptose region
The methylation analysis was used initially to determine the site of substitution of the carbamoyl radical. To do this, monosaccharide 3, disaccharide 12 and permethylated oligosaccharide were initially hydrolyzed with 0.5 ml of 2M trifluoroacetic acid (TFA, Merck) at 120° C. for 1 h. The N,N-dimethyl-7-O-carbamoyl radical is completely eliminated under these conditions. Excess TFA was stripped off by evaporation with distilled water in a rotary evaporator three times. The sample is subsequently reduced with sodium borodeuteride (NaBD 4 ) and acetylated, and the partially methylated deutero-reduced heptitol acetate is investigated by GC and GC-MS. 3.3. Assignment of the carbamoylheptose to the L-glycero-D-manno-heptitol and D-glycero-D-manno-heptitol configuration
All of the heptoses hitherto found in the LPS have, without exception, the L-glycero-D-manno-heptopyranose or D-glycero-D-manno-heptopyranose configuration. In order to be able to assign the 7-O-carbamoylheptose to one of these configurations, 4 mg of the LPS were dephosphorylated to LPS-HF. The 7-O-carbamoyl substituent was subsequently selectively eliminated under mild alkaline conditions (0.5M NaOH, room temperature, 30 min). We showed by kinetic studies that the carbamoyl radical is selectively eliminated under these conditions without involving damage to the heptose. Subsequently, hydrolysis (0.1M HCl, 48 h, 100° C.), reduction (5% NaBH 4 in 10 mM NaOH, overnight, room temperature) and peracetylation (Ac 2 O/pyridine) were carried out. Relative allocation of the configuration took place by means of GC analysis by comparison with the retention times of standard L-glycero-D-manno-heptitol and D-glycero-D-manno-heptitol which can easily be distinguished in the GLC as pairs of diastereomers. GC conditions: column SPB-5® (30 m, 0.25 mm, 0.25μ, Supelco); gradient: 150° C. for 3 min, then 5°/min to 330° C.
3.4. Screening process for determining 7-O-carbamoylheptose in dried bacteria
Dried bacteria (0.2 g) are suspended in 0.5 ml of 48% aqueous HF (Merck) and stirred vigorously at 4° C. in a Teflon vessel equipped with a Teflon stirrer overnight. The retentate from subsequent exhaustive dialysis against distilled water was freeze-dried. The 7-O-carbamoylheptose was then liberated from the LPS in the biomass by methanolysis (0.5M HCl/MeOH, 85° C., 30 min) and methylated Ciucanu, C. and Kerek, F., Carbohydr. Res., 131, (1984) 209-217! and the permethylated product was removed by centrifugation (3000 rpm, 15 min, Rotixa, Hettlich). The fatty acid methyl esters of lipoid A were subsequently removed using a small column (silica gel 60, 70-230 mesh, 0.5×30 mm, Merck) in 5 ml of ether/n-hexane (40:60), v/v) and then the product (3) was eluted with chloroform/methanol (C-M 95:5, v/v) and analyzed and quantified by GLC-MS on an SPB-5® column. The retention time (t R ) of the permethylated methyl-7-O-(N,N-dimethylcarbamoyl)-L-glycero-α-D-manno-heptopyranose anomeric structures (3α and 3β) was 17.76 min and 17.86 min respectively under the stated conditions (SPB-5®).
3.5. Isolation of 7-O-carbamoyl-LαD-Hepp-(1→3)-LαD-Hepp-(1→OMe), 9α, for NMR analysis
To isolate and prepare pure disaccharides 9α, initially 50 mg of LPS were hydrolyzed (0.1M HCl, 100° C., 85 min) and the precipitated lipoid A was removed by centrifugation. The supernatant was further purified on Sephadex G-10 (2.5×120 cm, water) and subsequently lyophilized. This core oligosaccharide was suspended in 4×0.5 ml aliquots in aqueous HF (48%, Merck) and vigorously stirred in Teflon vessels overnight. Drying at the oil pump (6 h) was followed by hydrolysis (0.5M HCl/MeOH, 85° C., 30 min) and the amino-containing components GalN and Ala were removed from the hydrolyzate on an ion exchanger (Amberlite IR-120, H + form). After the exchanger resin had been washed (50 ml), the H 2 O eluate was further purified by HPLC. The purified disaccharide 9α, which was found at R f =0.54 in TLC, eluted in the HPLC with a retention time of 21 min (yield of 9α, 1.23 mg).
3.6. Isolation of LαD-Hepp-(1→3)-LαD-Hepp-(1→OMe), 10α, and LαD-Hepp-(1→OMe), 2α, from the synthetic disaccharide LαD-Hepp-(1→3)-LαD-Hepp as reference substances for the NMR analysis
3.8 mg of the synthesized disaccharide 3-O(L-glycero-α-D-manno-heptopyranosyl)-L-glycero-D-manno-heptopyranose Paulsen, H. et al., Liebigs. Ann. Chem., (1986), 675-686) were incubated in 0.5M HCl/MeOH at 37° C. overnight. TLC analysis silica gel 60, chloroform/methanol/water (C-M-W) 100:100:30! revealed that, under these conditions, besides the target structure methyl-3-O-(7-O-carbamoyl-L-glycero-α-D-manno-heptopyranosyl)-L-glycero-α-D-manno-heptopyranose disaccharide (10α) (R f 0.40), there had also been partial formation of the monosaccharides methyl L-glycero-α-D-manno-heptopyranoside 2α (R f 0.58) and methyl L-glycero-β-D-manno-heptopyranoside 2β (R f 0.52). It was possible to separate these individual components in a subsequent HPLC run (Zorbax NH 2 , 9 250 cm, DuPont) with an increasing gradient from eluent A CH 3 CN--H 2 O 92:8 (v/v)! and eluent B CH 3 CN--H 2 O 50:50 (v/v)! at a flow rate of 3.5 ml/min. It was possible in this case to separate the disaccharide target structure 10α from the monosaccharides 2α and 2β, with the α-anomeric methyl glycosides showing a positive, and the β-anomeric methylheptose showing a negative, signal in the chiral detector. Aliquots of these peaks were tested once again by TLC (C-M-W 100:100:30). The purified disaccharide 9α (TLC R f =0.4) eluted in the HPLC with a retention time of 99 min, 2α (40 min, TLC R f 0.58) and 2β (54 min, TLC R f 0.52). The yields were: 10α, 0.81 mg, 2α 1.7 mg, 2β0.70 mg.
4. Results and discussion
To characterize the heptose required according to the invention, firstly the nature and position of the carbamoyl radical on the heptose were determined by means of various labeling experiments in the GC-MS analysis. Then the linkage of the two heptoses found in the core oligosaccharide of Pseudomonas aeruginosa PAC605 LPS and the substitution pattern of the carbamoyl radical in the disaccharide were likewise determined by GC-MS. Finally, the heptose disaccharide was isolated with the 7-O-carbamoyl radical on the heptose in intact form and underwent detailed analysis by one- and two-dimensional NMR spectrometry with 1 H- and 13 C-homo- ( 1 H, 1 H-COSY) and heteronuclear ( 1 H, 13 C-COSY) correlation. After the 7-O-carbamoyl-L-glycero-D-manno-heptopyranose had been identified, a screening process for determination thereof in bacteria was developed without previous extraction of the LPS.
4.1. GC-MS analysis of the 7-O-carbamoylheptose as per-O-acetylated derivative 5
Methanolysis (85° C., 2M HCl/MeOH, 30 min) of isolated, dephosphorylated core oligosaccharide from P. aeruginosa PAC605 LPS, per-O-acetylation and subsequent GC-MS analysis showed two different heptoses. One eluted as methyl 2,3,4,6,7-penta-O-acetylheptopyranoside (4) with a shorter retention time (t R =17.4 min) than a second, preivously unknown heptose derivative (t R =21.5 min). In the CI-MS, both heptoses showed a pseudo-molecular ion peak M+NH 4 ! + =452 (4) and M+NH 4 ! + =453 (5) (FIGS. 1 and 2). The difference in mass of one atomic mass unit (AMU) between 4 and 5, and the significantly increased retention time can be explained by the replacement of an acetyl radical (CO--CH 3 ) in 4 by a carbamoyl radical (CO--NH 2 ) in 5.
4.2. Identification of the carbamoyl group by GC-MS
To identify the carbamoyl group and determine its site of substitution, variously labeled derivatives of the unknown heptose were produced for the GC-MS analysis (3-8) in order to be able to prove the structure with this method.
4.2.1. GC-MS analysis of the permethylated 7-O-carbamoylheptose as mono- and disaccharide
After dephosphorylation and methanolysis, the methyl glycosides of the heptose were permethylated. It was possible in this case to identify the permethylated 7O-carbamoylheptose both as methyl 7-O-(N,N-dimethylcarbamoyl)-2,3,4,6-tetra-O-methylheptopyranoside (3) and as methyl 3-O- 7-O-(N,N-dimethylcarbamoyl)-2,3,4,6-tetra-O-methylheptopyranosyl!-2,4,6,7-tetra-O-methylheptopyranoside (12) in the GC-MS analysis (FIG. 3 and FIG. 4). Moreover the monosaccharide 3 showed in the EI-MS a characteristic fragment ion with m/z=320 M--OCH 3 ! + and m/z=146 which can be explained by the mass fragment HC=O + Me--CO--N(CH 3 ) 2 ! which derives from cleavage of the C-5/C-6 bond. This made it probable in the first place that the carbamoyl radical was a substituent on C-6 or C-7.
The disaccharide 12 (t R =34.3 min) (FIG. 4) showed in the EI-MS a mass fragment with m/z=320, which indicated that the carbamoyl substituent must have been located on the second, nonreducing heptose (Hep II). This interpretation is consistent with the existence of a mass fragment with m/z=263, which was assigned to the permethylated, reducing heptopyranose (Hep I). The results of the CI-MS support this interpretation ( M+NH 4 ! + =617, FIG. 4). It was possibly by perethylation in place of permethylation to convert monosaccharide 3 and disaccharide 12 into the relevant perethylated derivatives, it being possible to introduce 6 and 10, respectively, ethyl groups in place of the methyl group into 3 and 12, which was detectable in the MS analysis by a mass increment of Δm/z=14 AMU per ethyl radical introduced (detailed spectra not given here).
4.2.2. Labeling experiments and GC-MS analysis on 7-O-carbamoylheptose mono- and disaccharide
Methylation with iodomethane-d 1 in place of iodomethane allowed compound 6 to be identified as monosaccharide in the GC-MS analysis (FIG. 5). Once again, the characteristic M--OMe! + fragment with m/z=338 was observed, which corresponds to the fragment with m/z=320 in 3·m/z=155 was found analogously and was derived from cleavage of the C-5/C-6 bond. It was thus possible unambiguously to locate the carbamoyl group in position C-7 of the heptose from the fragment with m/z=107 CH═O--CO--N(CD 3 ) 2 ! which corresponds to the nondiagnostic m/z=101 CH═O--CO--N(CH 3 ) 2 ! in 3.
4.2.3. Reductive cleavage of the 7-O-carbamoyl radical using LiAlH 4
Compounds 7 and 13 were obtained by a mild and selective elimination of the permethylated carbamoyl radical from 3 and 12 respectively using LiAlH 4 in ether, and these have a free primary hydroxyl group in position 7 or 7' in place of the permethylated 7-O-carbamoyl group. Regioselective resubstitution of these free hydroxyl groups using N,N-dimethylcarbamoyl chloride in pyridine afforded the starting compounds 3 and 12 which did not differ in respect of retention time and mass fragmentation (EI-MS, CI-MS) from the initial substances. This provided a further indication of the postulated structure.
O-acetylation of 7 and 13 results in 8 and 14 respectively (FIG. 6 and FIG. 7), both of which show the charactertistic fragment with m/z=117 CHOMe--CH 2 --OAc! + which is derived from cleavage of the C-5/C-6 bond in the heptose. It was likewise possible to conclude from the fact that the mass fragment with m/z=263 was not changed either in the disaccharide 12 or in 14 that only the terminal heptose (Hep II) was substituted by the carbamoyl radical and that substitution on Hep I is precluded.
4.3. Methylation analysis of the heptose region in the core oligosaccharide
Monosaccharide 3 (3.5 mg) was hydrolyzed (2M TFA, 1 h, 120° C.), reduced (NaBD 4 ) and per-O-acetylated. We found that under these conditions the 7-O-carbamoyl radical is not quantitatively eliminated, and both 1,5,7-tri-O-acetyl-2,3,4,6-tetra-O-methylheptitol 15 (FIG. 9) and 1,5-di-O-acetyl-7-O- N,N-dimethylcarbamoyl!-2,3,4,6-tetra-O-methylheptitol 16 are obtained (FIG. 8). The partially methylated heptitol acetate 15 (t R =15.1 min, FIG. 9) showed in the CI-MS M+NH 4 ! + m/z=413 and M+H! + m/z=396 and in the EI-MS fragments with m/z=102 (162-60), 118 and 162 from deuterium-reduced end, and with m/z=117, 223 and 277 from the unreduced end. The partially methylated heptitol 16 (t R =19.7 min) showed in the CI-MS (FIG. 8) M+NH 4 ! + m/z=442 and M+H! + m/z=425 and in the EI-MS fragments with m/z=102 (162-60), 118, 162 from the deuterium-reduced end, and with m/z=102, 146, 262, 306 from the unreduced end. These mass fragments from the partially methylated heptitol acetates provided a further indication of 7-substitution by the carbamoyl radical.
The linkage of the two heptoses (HepII-Hep I) together was determined by methylation analysis of the permethylated disaccharide 12. 1,3,5,-Tri-O-acetyl-2,4,6,7-tetra-O-methylheptitol (18, t R =15.1 min, FIG. 10) was obtained, from which it was possible to determine the linkage of the heptoses together as Hepp-(1→3)-Hepp. The mass fragments (EI-MS) were at m/z=118, 234, 350 and were identified as fragments from the reducing end (FIG. 10). The data from the CI-MS analysis, M+NH 4 ! + with m/z=413 and M+H! + with m/z=396 are consistent with this interpretation.
On the other hand, carrying out the methylation analysis described above on the intact core oligosaccharide in place of the disaccharide revealed a 1,3,5-tri-O-acetyl-7-O-(N,N-dimethylcarbamoyl)-2,4,6-tri-O-methylheptitol 17 with a retention time of 24.5 min. The existence of a 3-O-acetylated 7-O-carbamoylheptitol in 17 can be explained by substitution of the GalN Ala! residue in position 3 of Hep II in the intact core oligosaccharide. This result is consistent with data obtained earlier by Rowe and Meadow Rowe, P. S. N. and Meadow, P. M., Eur. J. Biochem., 132 (1983) 329-337! and E. Altman et al. (E. Altman et al., Biochemistry 1994, submitted for publication; E. Altman et al., Int. Carb. Conference, Paris 1992, Abstract Book C161, p. 626; H. Masoud et al., 2nd Conference of the International Endotoxin Society (IES), Vienna 1992, 69, p. 55), who had determined the site of substitution of GalN-Ala and the linkage of the heptoses with one another likewise as GalpN Ala!-(1→3)-LαD-Hepp-(1→3)-LαD-Hepp.
4.4. Assignment of the 7-O-carbamoylheptose to the L-glycero-D-manno or D-glycero-D-manno configuration
Measured first in the GLC analysis (SPB-5®) was a standard which contained both peracetylated D-glycero-D-manno-heptitol (D,D-Hep-ol) and L-glycero-D-manno-heptitol (L,D-Hep-ol) (t R =21.36 min, D,D-Hep:t R =21.89 min, L,D-Hep). After the 7-O-carbamoyl radical on Hep II had been selectively removed from the core oligosaccharide of P. aeruginosa PAC605 by mild alkaline hydrolysis, the heptitol acetates prepared from Hep I and Hep II in this was were investigated in GC analysis. It emerged that only L-glycero-D-manno-heptitol acetate was detectable, t R =21.89 min, which corresponds to L,D-Hep-ol (FIG. 12). This experiment and the fact that the heptose remains intact on elimination of the carbamoyl substituent made it probable that the 7-O-carbamoylheptopyranose (Hep II) has the L-glycero-D-mannoheptose configuration (compare also NMR analysis).
4.5 NMR analysis of the methyl-3-O-(7O-carbamoyl-L-glycero-α-D-manno-heptopyranosyl)-L-glycero-α-D-mannoheptopyranose 9α
4.5.1. 1 H-NMR analysis
The disaccharide 3-O-(7-O-carbamoyl-L-glycero-α-D-manno-heptopyranoysl)-L-glycero-.alpha.-D-manno-heptopyranose 9α was isolated after mild methanolysis from the dephosphorylated core oligosaccharide and was purified by HPLC. The results of the proton NMR analysis are depicted in FIG. 13 and Table 1. It is significant that there is a low-field shift of the signals for H-7'a and H-7'b by about 0.3 ppm (4.085 and 4.154 ppm) in 7-O-carbamoylheptose compared with the analog signals for H-7a and H-7b in the unsubstituted heptose (3.7276 and 3.751 ppm respectively). Substitution in position 3 of Hep I is manifested only by a low-field shift of about 0.12 ppm compared with the α-anomeric methyl L-glycero-D-manno-heptopyranoside 2α. All the other signals agree well with the synthetic disaccharide methyl-3-O-(L-glycero-α-D-manno-heptopyranosyl)-L-glycero-α-D-manno-heptopyranose (10α). The good agreement of the signals is a further indication of the L-glycero-α-D-manno configuration found in the GC analysis.
4.5.2 13 C-NMR analysis of disaccharide 9α
The results of the 13 C-NMR analysis derived from the spectra with heteronuclear correlation for the disaccharide 3-O-(7-O-carbamoyl-L-glycero-α-D-manno-heptopyranosyl)-L-glycero-.alpha.-D-manno-heptopyranose (9α) are to be found in FIG. 14 and Table 2. Comparison with the synthetic disaccharide methyl-3-O-(L-glycero-α-D-manno-heptopyranosyl)-L-glycero-α-D-manno-heptopyranose (10α) and the synthetic monosaccharide methyl L-glycero-α-D-manno-heptopyranoside (2α) made it possible to deduce the individual structural features of the heptose (7-O-carbamoyl substitution, glycosidic linkage and configuration). The carbonyl CI--NH 2 signal at 159.86 ppm is particularly noteworthy and agrees well with an analog signal (159.6 ppm) for a 6-O-carbamoyl-GlcN(Me: 18:0)-R from Azorhizobium caulinodans which was recently described (Mergaert, P. et al., Proc. Natl. Acad. Sci. USA, 90 (1993) 1151-1555). The low-field shift of the signal for C-7' in 9α is only about 2.2 ppm by comparison with the unsubstituted compound 10α, which is not unusual for glycosidic substituents on primary hydroxyl groups. On the other hand, the low-field shift of C-3 on Hep I (71.35 vs. 77.89 ppm) is significant, which again confirms the Hep-(1→3)-Hep substitution in the disaccharide. All the other signals agree well with the disaccharide 10α. The good agreement of the 13 C signals with the synthetic reference compounds 2α and 10α is a further indication of the L-glycero-α-D-manno configuration found in both heptoses.
4.6 Laser desorption mass analysis (LD-MS) of the methyl-3-O-(7-O-carbamoyl-L-glycero-α-D-manno-heptopyranosyl)-L-glycero-α-D-manno-heptopyranose 9α
The result of the laser desportion mass analysis of compound 9α is depicted in FIG. 15. The molecular weight of the methyl-3-O-(7-O-carbamoyl-L-glycero-α-D-manno-heptopyranosyl)-L-glycero-α-D-heptopyranose (9α) was calculated for the molecular formula C 18 O 14 H 29 N as 459.40. The LD-MS spectrum showed the purified disaccharide 9α as a unique pseudomolecular peak with a molar mass of M+Na! + =459+23=482 and is thus in excellent agreement with the calculated structure shown.
TABLE 1______________________________________Chemical shift, assignment and coupling constants for the signals in the.sup.1 H-NMR spectrum of methyl-7-O-carbamoyl-LαD-Hepp-(1→3)-LαD-Hepp-(1→OMe) 9α compared with the syntheticLαD-Hepp-(1→3)-LαD-Hepp-(1→OMe) 10α and LαD-Hepp-(1→OMe)2α referencecompounds (360 MHz, D.sub.2 O, room temperature).______________________________________7-O-carbamoyl-LαD-Hepp-(1→9α 10αδ (ppm) J (Hz) δ (ppm) J (Hz)______________________________________H-1' 5.197 1.3 5.150 1.7H-2' 4.093 2.6 4.071 3.1H-3' 3.913 6.2 3.894*H-4' 3.703 5.7 3.894* 9.8H-5' 3.709 1.3 3.705 1.9H-6' 4.228 7.9 4.052 5.4H-7'a4.085 10.5 3.729 11.9H-7'b4.154 6.2 3.760 6.8______________________________________→3)-LαD-Hepp-(1→OMe) 2α______________________________________H-1 4.717 1.3 4.747 1.9 4.737 1.5H-2 3.983 3.5 4.031 3.2 3.895 3.4H-3 3.906 10.3 3.842 9.9 3.729 9.8H-4 3.983 9.7 3.967 10.0 3.825 10.2H-5 3.600 1.5 3.604 1.6 3.544 1.9H-6 4.055 6.8 4.048 5.8 4.015 5.8H-7a 3.727 11.6 3.662 11.4 3.685 11.1H-7b 3.751 6.9 3.741 7.4 3.731 7.3OMe 3.370 3.389 3.380______________________________________ *unresolved multiplet
TABLE 2__________________________________________________________________________Chemical shift and assignment of the .sup.13 C-NMR signals of7-O-carbamoyl-LαD-Hepp-(1→3)-LαD-Hepp-(1→OMe) 9α, compared withsynthetic reference compoundsLαD-Hepp-(1→3)-LαD-Hepp-(1→OMe) 10α andLαD-Hepp-(1→OMe) 2α.__________________________________________________________________________ α (ppm) 9α 10αC atom 7-O-carbamoyl-LαD-Hepp-(1→ LαD-Hepp-(1→__________________________________________________________________________C-1' 103.06 103.30C-2' 70.83 70.91C-3' 71.33 71.35C-4' 66.89 66.70C-5' 72.09 72.63C-6' 66.69 69.51C-7' 65.90 63.68--O--CO--NH.sub.2 159.86__________________________________________________________________________ 2α →3)-LαD-Hepp-OMe →3)-LαD-Hepp-OMe LαD-Hepp-OMe__________________________________________________________________________C-1 101.77 101.75 103.30C-2 70.70 70.56 70.91C-3 77.89 70.09 71.35C-4 66.73 66.45 66.64C-5 72.26 72.04 72.04C-6 69.48 69.64 69.51C-7 63.73 63.68 63.68__________________________________________________________________________ *(D.sub.2 O, 90.556 MHz, ppm relative to internal acetonitrile 1.700 ppm)
TABLE 3______________________________________Identification of the 7-O-carbamoylheptose in the coreoligosaccharide from various Gram-negative bacteria7-O-carbamoylheptopyranose______________________________________1. Pseudomonadaceae (old classification)1.1 Rough form mutantsPseudomons aeruginosa PAC605 +P. aeruginosa PAC 557 +P. aeruginosa PAC1R +P. aeruginosa RS (Habs 6) +1.2. Smooth form bacteriaP. aeruginosa Fischer 2 immunotype +P. aeruginosa Fischer 7 immunotype +P. aeruginosa 170519 +P. aeruginosa 170520 +P. aeruginosa FH-N-845 +P. fluorescens ATCC 49271 +Pseudomonas plantarii DSM 712B -2. Non-PseudamonadaceaeKlebsiella pneumoniae, K 25 -Yersinis enterocolitica, mutant 490 M -Campylobacter jejuni RN16 O:58, CCUG 10936 -Proteus mirabilis mutant R.sub.45 -Haemophilus influenzae, wild-type, Eagan strain -Vibrio parahaemolyticus, serotype O12 -Salmonella minnesota SF 1111 (S form) -Escherichia coli O111 (S form) -______________________________________ | The invention describes 7-O-carbamoyl heptose derivatives of general formula (I) in which R is the substituent R 1 or a group of general formula (II) in which R 1 is a hydrogen atom, a methyl group or a suitable linker substituent suitable for a covalent coupling, a process for their production and their use in producing reagents and compositions for the diagnosis and therapy of pseudomona infections in humans and animals, and a screening process for their detection in Gram-negative bacteria. ##STR1## | 2 |
This is a regular patent application claiming priority under 35 U.S.C. 119 (a) to Mexican Patent Application No. MX/a/2015/007857 filed on Jun. 18, 2015 for a system and method to decrease the viscosity of the crude oil and the empowerment of their dehydration.
The present invention relates to a method for treating crude oil (hereinafter may be referred to only as “crude”) in a way that (a) crude oil maintains one viscosity less than a given temperature and (b) strengthen the methods for the removal of water (dehydration). Low viscosity allows oil to be maintained in a liquid state and fluid at low temperatures and without heat, when normally it would not be so. As for the decrease of viscosity, this eliminates the need for heating oil in order to pump it and transport it steadily and even for certain crude, can eliminates the need to use chemicals flow improvers. With regard to the dehydration of crude oil, it potentates the effect of emulsion compatible with the technology described here and specific chemicals.
BACKGROUND OF THE INVENTION
It is well known that most of the crude is heavy and the handling and transportation of these is a complicated issue, which involves high costs. In addition, to extract crude from an oil well, usually extracted first light crude or less heavy, leaving the final extraction of crude heavy, extra heavy and ultra heavy, so, with the passage of time the trend towards how ruling the latter, will be higher. Now, to improve the extraction of crude oil, many wells are assisted by injecting dry steam or water to promote an improvement in the production of oil wells, however, causing crude oil containing one higher percentage of water to the be removed, what it ends up turning into a complication. An aspect of the present invention, is to avoid the current practice of heating of crude oil during all processes of handling or transportation of this until it is used or stored, in turn, help enhance the methods of disposal of the crude water (both congenital and added).
Crude oil is a hydrocarbon normally high viscosity that requires temperature between 50° C.-80° C. to pump it or transport it from the source to its final destination. In the majority of occasions, chemicals flow improvers are used for the facilitation of this work.
Now, in regards to the water contained in the crude oil, both congenital and added, the percentages can occur practically in any proportion (from 10% or less, up to 70% or more).
What is sought with the present invention is to eliminate or significantly reduce many of the costs involving the heating of crude oil and the use of chemical products for improvement of flow or dehydration (emulsion breakers), while the same processes become more efficient.
Keep warm crude during all line transport, storage tanks and chemicals flow and dehydrators improvers, involves a considerable cost. Add to this the penalty for exceeding the maximum percentage of water and salt allowed as an international standard for selling oil and the decline for crude oil that is left in the tanks; Since the heating methods cannot ensure provide heat to the entire contents of the tanks. You can understand that the figure rises, but we are certain that can greatly be reduced through the use of the present invention.
OBJECTS OF THE INVENTION
It is the object of the present invention, to treat crude oil with a device disposed in a crude oil supply line so that (a) crude oil maintains one viscosity less than a given temperature and (b) potentiates the methods for dehydration. Low viscosity allows oil to be maintained in a liquid state and fluid at low temperatures and without heat, when normally it would not be so.
The device that is used to treat crude oil consists of 2 parts: a metal casing tube-shaped, designed to connect directly to the line of transportation of crude oil pipeline and a center or core in its interior, which consists of five different in a unique configuration and design metals (see FIG. 8 ), which allows crude is agitated or swirling as it gets in contact with the core by activating the electrostatic charge by means of friction.
Derived from the electrostatic charge induced on the crude, this invention produces an ionization-polarization in molecules of crude oil, achieving lower viscosity, so that it is able to maintain a liquid state so it can be manipulated or transported without heating. This same ionization-polarization in crude oil molecules facilitates the release of congenital or added water contained in it, thus potentiating the physical and chemical methods used for this purpose, when the chemicals are compatible with this invention.
BRIEF SUMMARY OF THE INVENTION
The present invention is a method for viscosity decrease in crude oil and the potentiating of dehydration, passing oil on a core that polarizes an electrostatically charged. The core consists of a metal bar made of an alloy, which includes, by weight, 40-70% copper, 10-32% nickel, 15-40% zinc, 2-20% tin, and 0.05-10% silver. The core is within a housing having an inlet and an outlet at their ends to receive and download the crude is to be treated. The Center or core is disposed in a crude oil supply line. The metal bar of the core comprises a plurality of cuts that have a concave shape and arranged diagonally along an entire surface of an upper and lower face of the metal bar of the core to create grooves, which allows crude oil to be agitated as it comes in contact with the core, activating the electrostatic charge.
The electrostatic charge generated by the core, create a magnetic catalytic reaction that causes a molecular alignment in crude oil molecular chains, thus reducing the viscosity of the same. The lower viscosity maintains crude oil in a liquid state for pumping and transport. The electrostatic charge generated by the core creates a magnetic catalytic reaction that causes a lengthening/stretching in the crude oil molecules, this coupled with the ionization-polarization thereof, creates a kind of molecular torsion that helps crude oil to release the water molecules trapped in it.
This occurs because the atoms of the metals have a very broad spectrum of electrons around its core, which affects the molecules and atoms of other elements that come in contact with them, for our particular case, molecules and atoms of the crude oil and the elements contained in it (water and salt).
Theory tells us that the molecular ionization-polarization process produces disorganization and breakdown of the particles responsible for the formation of gel (conglomerate), which leads to an improvement in the flow of crude oil. As a result, it is possible for crude oil to remain fluid at temperatures of 0° C.
In a crude oil that has not been ionized-polarized, aromatic tend to attract electrostatically (called pi-pi stacking effect) and due to the planarity of aromatic rings, are capable of Covalent not each other. Finally, this; results in a structure stabilized and strengthened through additional links. These links can be easily broken, especially through the effects of temperature (above 90° C.).
However, when crude oil is heated and polarized, the aromatics are not able to interact freely with each other and prevents the formation of the effect of pi-pi stacking Instead, a homogeneous mixture of aromatic and paraffin is formed. The structure formed by this mixture of aromatics and paraffin, not stabilized or reinforced by links additional non-Covalent and that is the reason why crude oil can stay liquid or fluid at lower temperatures.
Having this crude oil weakened structure, additionally contributes to the molecules of the same release the external elements contained in them (water mainly), which enhances the efficiency of the chemicals for disposal (dehydration).
BRIEF DESCRIPTION OF THE DRAWINGS
Further objects and advantages of the present invention can be found in the detailed description of the preferred embodiments when taken in conjunction with the accompanying drawings in which:
FIG. 1A is the molecular chain of the crude oil before to treatment.
FIG. 1B is the molecular chain of crude oil after a treatment.
FIG. 1C is an electron microscope spectral analysis of the chain of crude oil after treatment.
FIG. 2 is is the differential scanning calorimetry temperature log of the crude control sample.
FIG. 3 is the differential scanning calorimetry temperature log of the control crude sample with marked cycles of cooling and heating.
FIG. 4 is the differential scanning calorimetry temperature log of the control of ionized-polarized crude sample with marked cycles of cooling and warming.
FIG. 5 is the differential scanning calorimetry temperature log of the control of polarized crude oil sample 2 with marked cycles of cooling and heating.
FIG. 6 is the differential scanning calorimetry temperature log of the control of crude oil ionized-polarized sample 1 and crude-ionized-polarized sample 2.
FIG. 7 is part of the differential scanning calorimetry temperature log showing heating for the control bunker sample, of ionized-polarized crude sample 1 and ionized-polarized crude sample 2.
FIG. 8 is a demonstrative image with ionizer-polarizing device, where you can see Shell and core (Center).
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Crude oil is treated with a core prepared in a crude oil supply line so that (a) crude oil maintains one viscosity less than a given temperature and (b) potentiates the methods for dehydration. The core is disclosed in U.S. Pat. No. 6,712,050. The core being used to treat crude oil consists of five different metals in a unique and patented arrangements of grooves, which allows crude oil to be agitated or swirl as it comes in contact with the core, activating the electrostatic charge. The core is made of an alloy comprising, by weight, 30-60% copper, 10-30% nickel, 15-40% zinc, 5-20% tin, and 1-10% silver. The core is in a closed tube, which is directly connected to the crude oil supply, preferably at the production site.
When oil is passed through the device and it frictions with the core, constant magnetic field is created affecting the molecules of the oil. The crude acts as a dielectric, which creates an ionization-polarization. The effect blends the hydrocarbons and alkanes. Additionally, the water in the crude oil usually contains a high amount of salt, which is released, therefore acts as an excellent conductor of electricity. When crude oil comes out of the core having been subjected to the magnetic field, ionization-polarization and molecular refraction, the crude's molecular geometry and viscosity have been significantly modified and will remain low even in temperatures below 15° C. In fact, tests have shown treated crude oil remaining in the liquid state in temperatures above 0° C.
The device disposed in the supply of crude oil line does not consume any extra energy. As shown in FIGS. 1A, 1B and 1C as the crude passes over the core, electrostatically charged molecules with the same polarity adheres to the thesis of mutual rejection and thus creates a finer structure of the molecular of crude oil chain. FIG. 1A depicts the molecular crude oil chain before passing over the core, which is herein also called treatment. FIG. 1B depicts the molecular crude oil chain after treatment. FIG. 1C is an electron microscope spectral analysis of crude oil after treatment. The outgoing liquid, or ionizer-polarized liquid, which has a finer structure, can be transported to the consumer, or pumped into transport vessels without any further treatment or heating, there by revolutionizing the cost structure for creation and of crude oil.
Crude oils are a compound of linear, cyclic, aromatic alkanes, water, salts, some metals and sulfur. The ratio of these components is diverse and there is no general pattern: each deposit is particular in its composition of molecules. The real constant is that crude oil is kept flowable, that is to say has the viscosity that allows it to flow easily in temperatures above 60° C. When lowering the temperature, the intermolecular energy diminishes causing them to contract, inducing this increase of viscosity.
As discussed, viscosity is closely connected with the order of the molecules within the liquid and their interaction with the surface of the liquid (surface tension). The effects of a magnetic field on the properties of the liquids have been studied; this branch of physics is known as magnetohydrodynamics. A magnetic field represents or is a manifestation of energy, and if we take into consideration the magnetic nature of organic molecules (covalent), it is expected that in the proportion of the intensity of the magnetic field the shape of the molecules is altered. The Stereoisomerism explains how a compound with the same molecular weight and the same atom proportions, can present different physical and chemical properties.
In the case of the core, the magnetic field is generated in cylindrical core-carrying chamber. This magnetic field is constant and permanent, and affects the “empty” spaces of the organic molecules of the crude oil passing through and over and around the core. Furthermore, crude oil acts as a dielectric member (a material that conducts electric energy poorly) which generates a polarization in it, a fact that prompts a “bending” of the alkanes (cyclical and linear). During this process, encapsulated water with a high salt content is released, and therefore the water release acts as an excellent conductor of electricity.
When these forces act on the liquid crude oil (magnetic field, polarization) by orientation, molecular refraction-Intermolecular forces of crude oil before passing through the center of ionization-polarization, crude oil is reorganized with “new” (mainly of the type Van der Walls) Intermolecular forces; crude oil has changed its molecular geometry and, in this process, the viscosity of the treated crude remains low even at temperatures below 15° C. In addition, testings have shown that treated oil remains in a liquid state at temperatures around 0° C. We must consider that the intensity of the magnetic field (and its side effects) cause the “separation” of radical. Evidence of the testing indicates that treated oil has an effect on the content of salts, sulphur and composition thereof.
EXAMPLE I
Three crude oil samples were received: (1) oil control, (2) ionized-polarized oil sample 1 and (3) crude ionized-polarized sample 2. The three samples were examined with differential scanning calorimetry (hereinafter referred to as “DSC”) by using “DSC823e Mettler Toledo”, device, the results of which are shown in FIGS. 2 to 7 . The basic principle underlying this technique is that when the sample undergoes a physical transformation such as phase transitions, more or less heat will be need to flow to it than the reference to maintain both at the same temperature. Whether less or more heat must flow to the sample depends on whether the process is exothermic or endothermic. For example, as a solid sample melts to a liquid, it will require more heat flowing to the sample to increase its temperature at the same rate as the reference. This is due to the absorption of heat by the sample as it undergoes the endothermic phase transition from solid to liquid.
Measurement was conducted in four levels of cooling and three levels of heating with speed of 10° C./min in nitrogen environment: (1) cooling 25° C. to −40° C., (2) heating from −40° C. to 25° C., (3) cooling from 25° C. to −40° C., (4) heating from −40° C. to 100° C., (5) cooling from 100° C. to −40° C., (6) heating of −40° C. to 100° C., (7) cooling from 100° C. to 25° C. In FIGS. 2-7 , the x axis reflects the temperature and the y axis reflects the heat flow or power differential (mW). Example of one complete temperature log, with all measuring cycles, is shown in FIG. 2 . FIG. 3 shows a DSC temperature log of crude oil of sample with marked cycles of cooling 1, 3, 5 and 7 and heating 2, 4 and 6. FIG. 4 shows a DSC temperature log of crude oil sample 1 with marked cycles of cooling 1, 3, 5 and 7 and heating 2, 4 and 6. FIG. 5 shows DSC temperature log of crude oil sample 2 with marked cycles of cooling 1, 3, 5 and 7 and heating 2, 4 and 6.
FIG. 6 shows a DSC temperature log of all three (3) samples showing cooling. Control crude oil 10 , ionized-polarized sample 1 11 , and ionized-polarized crude oil sample 2 12 are shown being cooled at four temperatures. The samples were cooled from 100° C. to 25° C. The results of this cooling is shown as crude 10 a , ionized-polarized control oil sample 1 11 a and ionized-polarized crude oil sample 2 12 a . The samples were cooled from 100° C. to −40° C. The results of this cooling are shown as control crude oil 10 b , ionized-polarize sample 1 11 b and ionized-polarized crude oil sample 2 12 b . The samples were cooled from 25° C. to −40° C. The results of this cooling is shown as control crude oil 10 c , ionized-polarized sample 1 11 c , and ionized-polarized crude oil sample 2 12 c . The samples were heated and cooled again from 25° C. to −40° C. The results of this cooling are shown as crude oil 10 d , ionized-polarized sample 1 11 d and ionized-polarized crude oil sample 2 12 d.
FIG. 7 shows the DSC temperature log of all three (3) samples showing heating. Control crude oil ( 10 ), ionized-polarized crude oil sample 1 ( 11 ), and ionized-polarized crude oil sample 2 ( 12 ) are shown being heated at three temperatures. The samples were heated from −40° C. to 25° C. The results of this heating are shown as control crude oil ( 10 e ), ionized-polarized crude oil 1 sample ( 11 e ) and ionized-polarized crude oil sample 2( 12 e ). The samples are heated from −40° C. to 100° C. The results of this heating is shown as control crude oil (100, ionized-polarized crude oil sample 1 (110 and ionized-polarized crude oil sample 2( 12 f ). The samples were cooled and heated again from −40° C. to 100° C. The results of this heating is shown as control crude oil sample ( 10 g ), ionized-polarized crude oil sample 1 ( 11 g ) and ionized-polarized crude oil sample 2 ( 12 g ). In general, these DSC temperature logs show that control crude oil reflects a higher heat flow than the ionized-polarized crude oil samples. This is likely due to higher viscosity and a more complex molecular structure in the control crude oil sample than in the sample of ionized-polarized crude oil sample.
EXAMPLE II
The primary goal of the test was to determine the changes in the crude oil molecular structure when treated with the core. The method and the resulting treated crude oil was tested at INA d. d. Zagreb Croatia in Petroleum Products Quality Control Laboratory (wee www.ina.hr) and became evidence of ratification of decrease of viscosity and potentiation of dehydration by Comercializadora Teotihuitzu, S.A. de C.V. in Mexico.
Once signs of crude passed through the device object of this invention mounted on a bypass in the supply line, the collection process determined that the viscosity of the samples was less than the viscosity of Control crude oil (untreated crude).
The purpose of the testing was to establish potential differences between the untreated oil and crude oil treated with the device. The test was run in crude oil samples, which passed through the ionizer-polarizer device and oil samples from a reservoir in Kalinovici. In total, 2 samples of untreated crude oil and 2 samples of treated crude oil were processed for purposes of testinging of Croatia. For ratification testing in Mexico, were 2 samples of oil from the well of Samaria production 709 , 2 samples of oil from the well of Samaria production 848 and 1sample of assets of Pemex Samaria II of head #93. 5 samples were treated and processed to determine decrease viscosity and dehydration, the results in Mexico were obtained and certified by Intertek Testing Services de Mexico, S.A. de C.V. (Results: Sample 709 : 60% water mass as control; 55.7% water mass with ionizer only; 1.09% water mass with ionizer and chemical dehydrator. Sample 848 : 2.14% water mass as control; 5.11% water mass with inionizer only; 1.34% water mass with ionizer and chemical dehydrator. Sample 93 : 6.22% water mass as control with dehydrator chemical; 1.25% water mass with ionizer and chemical dehydrator.) Two methods were used for testing in Croatia: (a) SEM (scanning electron microscope) which is a microscopic observation of the surface of the crude oil and (b) DSC (differential scanning calorimetry) a thermal method that determines the specific heat of the crude oil. Two methods were used for testing of ratification in Mexico: (a) kinematic viscosity and(b) water in crude oil by potentiometric titration of Karl Fischer. Tables IV to IX show the results of initial testing performed on samples to show their inherent properties.
TABLE IV
Quality Control for Ionized-Polarized Crude Oil Sample
Features
Units
Cutoff
Result
Method
Carbon residue
—
HRN EN ISO 10370
MICROCARBON
Carbon residue on
% m/m
<15
2.56
HRN EN ISO 10370
overall sample
Ash (oxide) -
% m/m
<0.2
0.177
HRN EN ISO
instrumental method
6245
Flash point closed,
° C.
>70
124.5
ASTM D 93: 10 (A
PM
procedure)
Pour point
° C.
<40
36
HRN ISO 3016: 97
Kinematic viscosity
—
ASTM D 7042: 10
at certain temperature
Kinematic viscosity
mm 2 /s
6-26
24.58
ASTM D 7042: 10
at 100° C.
Sulfur wave-
% m/m
<1
0.93
ASTM D 2622
dispersive X-Ray
TABLE V
Two-Dimensional Gas Chromatography for Ionized-
Polarized Crude Oil Sample Quality Control
Features
Units
Cutoff
Result
Method
GCxGC - Comprehensive
Own method
Two-dimensional gas
(for GCxGC)
chromatography (determining
group composition in
petroleum and middle
distillates, diesel fuel
and light cyclic oils)
Paraffins - total
% m/m
47.79
Own method
(for GCxGC)
n- paraffins
% m/m
16.95
Own method
(for GCxGC)
iso-paraffins
% m/m
14.01
Own method
(for GCxGC)
cyclo-paraffins - naphthenic
% m/m
16.83
Own method
(for GCxGC)
Paraffins (n-; iso-)
% m/m
30.96
Own method
(for GCxGC)
Olefins
% m/m
Own method
(for GCxGC)
Arenes - total
% m/m
52.21
Own method
(for GCxGC)
mono-arenes
% m/m
11.74
Own method
(for GCxGC)
di-arenes
% m/m
30.34
Own method
(for GCxGC)
tri-arenes
% m/m
10.13
Own method
(for GCxGC)
poly-arenes
% m/m
40.47
Own method
(for GCxGC)
Biphenyls
% m/m
Own method
(for GCxGC)
TABLE VI
Quality Control for Ionized-Polarized
Oil Sample at 100° C. (4 months old)
Features
Units
Cutoff
Result
Method
Carbon residue
—
HRN EN ISO 10370
MICROCARBON
Carbon residue on
% m/m
<15
<0.01
HRN EN ISO 10370
overall sample
Ash (oxide) -
% m/m
<0.2
<0.001
HRN EN ISO 6245
instrumental method
Flash point closed,
° C.
>70
118.5
ASTM D 93: 10 (A
PM
procedure)
Pour point
° C.
<40
0
HRN ISO 3016: 97
Kinematic viscosity
—
ASTM D 7042: 10
at certain temperature
Kinematic viscosity
mm 2 /s
6-26
23.51
ASTM D 7042: 10
at 100° C.
Sulfur wave-
% m/m
<1
0.9
ASTM D 2622
dispersive X-Ray
TABLE VII-V
Two-Dimensional Gas Chromatography- Quality Control
for Ionized-Polarized Crude Oil Sample(4 months old)
Features
Units
Cutoff
Result
Method
GCxGC - Comprehensive
Own method
Two-dimensional gas
(for GCxGC)
chromatography (determining
group composition in
petroleum and middle
distillates, diesel fuel
and light cyclic oils)
Paraffins - total
% m/m
48.73
Own method
(for GCxGC)
n- paraffins
% m/m
21.47
Own method
(for GCxGC)
iso-paraffins
% m/m
13.78
Own method
(for GCxGC)
cyclo-paraffins - naphthenic
% m/m
13.48
Own method
(for GCxGC)
Paraffins (n-; iso-)
% m/m
32.25
Own method
(for GCxGC)
Olefins
% m/m
Own method
(for GCxGC)
Arenes - total
% m/m
51.27
Own method
(for GCxGC)
mono-arenes
% m/m
12.34
Own method
(for GCxGC)
di-arenes
% m/m
28.83
Own method
(for GCxGC)
tri-arenes
% m/m
10.1
Own method
(for GCxGC)
poly-arenes
% m/m
38.93
Own method
(for GCxGC)
Biphenyls
% m/m
Own method
(for GCxGC)
TABLE VIII
Quality Control for Ionized-Polarized Crude
Oil Sample to 110° C. (4 months old)
Features
Units
Cutoff
Result
Method
Carbon residue
—
HRN EN ISO 10370
MICROCARBON
Carbon rescue on
% m/m
<15
<0.01
HRN EN ISO 10370
overall sample
Ash (oxide) -
% m/m
<0.2
<0.001
HRN EN ISO 6245
instrumental method
Flash point closed,
° C.
>70
116.5
ASTM D 93: 10 (A
PM
procedure)
Pour point
° C.
<40
6
HRN ISO 3016: 97
Kinematic viscosity
—
ASTM D 7042: 10
at certain temperature
Kinematic viscosity
mm 2 /s
6-26
23.48
ASTM D 7042: 10
at 100° C.
Sulfur wave-
% m/m
<1
0.9
ASTM D 2622
dispersive X-Ray
The table IX—Quality Control for Ionized-Polarized Crude oil Sample at 110° C.(4 months old)
The table IX- Quality Control for Ionized-Polarized
Crude Oil Sample at 110° C. (4 months old)
Features
Units
Cutoff
Result
Method
Carbon residue
—
HRN EN ISO 10370
MICROCARBON
Carbon residue on
% m/m
<15
<0.01
HRN EN ISO 10370
overall sample
Ash (oxide) -
% m/m
<0.2
<0.001
HRN EN ISO 6245
instrumental method
Flash point closed,
° C.
>70
116.5
ASTM D 93: 10 (A
PM
procedure)
Pour point
° C.
<40
3
HRN ISO 3016: 97
Kinematic viscosity
—
ASTM D 7042: 10
at certain temperature
Kinematic viscosity
mm 2 /s
6-26
23.17
ASTM D 7042: 10
at 100° C.
Sulfur wave-
% m/m
<1
0.9
ASTM D 2622
dispersive X-Ray
SEM Testing—Scanning Electron Microscope
For the purpose of SEM testing, a microscope JEOL 5800 was used, equipped with corresponding detectors. One of the important conditions for this SEM test is that the sample needs to be stable in high vacuum. To ensure stability, a drop of crude oil was disposed on a glass smeared, to get as thin and homogeneous smear as possible. The smear was dried and gold plated to ensure good electrical transmittance and therefore a better image. Cavities or holes were spotted, smaller and bigger. For the crude oil samples that had passed through the ionizer-polarizer core, the number of those cavities or holes was significantly greater. Particles' sizes were between 10-30 m. Particles were not usually spotted with crude oil treated with the ionizer-polarizer core, but only the cavities of different size and shapes.
DSC Testing
This testing was conducted with Perkin Elmer DSC-7 calorimeter. Testing was done within the temperature range of 30° C. to 150° C., recording speed of 10° C./min in oxygen current. Small amounts of sample weighing a few milligrams were measured.
In conclusion, the test has shown that certain significant difference exists between untreated crude oil and crude oil treated with the ionizer-polarized core. Namely, the viscosity of the treated crude oil was lowered such that the crude oil maintained a liquid state without heat. Moreover, the treated samples had a significant reduction in the content of sulfur contaminants. The tests confirmed that exposure of the crude oil in liquid to the core, changed the crude oil liquid point from 30° C. to 0° C. The volatility or flash point decreased from 124.5° C. to 116.5° C.
Based on previous experience on exposing crude oil to the ionizer-polarized core which creates catalytic reactions, it was concluded that the reaction causes molecular separation with an electric charge. Because of molecular separation and the electric charge, mass changes and reflection or repulsion of particles with the same charge leads to changes in the physical performance like liquefaction and lower viscosity.
While crude oil passes over the ionizer-polarizer device because of the present invention, the electrostatically charged molecules of crude oil now with the same polarity repel each other and thus create a finer structure in the molecular chain of crude oil. This fine structure allows that treated oil being transported or pumped more easily and involving lower costs.
The claims appended hereto are meant to cover modifications and changes within the scope and spirit of the present invention. | A method and system for reducing viscosity in the crude oil and the empowerment of its dehydration process pass crude oil over a core that ionizes-polarizes the crude oil with an electrostatic charge. The metal bar core made of an alloy which includes, a weight of, 40-70% copper, 10-32% nickel, 15-40% zinc, 2-20% tin, and 0.05-10% silver. The metal bar core comprises a plurality of grooves, which allows crude oil to be agitated as it comes in contact with the core, activating an electrostatic charge. The electrostatic charge of the core creates a magnetic catalytic reaction that causes: (1) a molecular separation in the molecular chains within crude oil thereby lowering the viscosity and (2) stretches and twists caused by the molecular ionization-polarization of crude oil, causes that this release accordingly congenital or added water that is trapped in it, resulting in a potentiation of the dehydration of crude oil. | 2 |
CROSS REFERENCES TO RELATED APPLICATIONS
The present application is a Continuation of U.S. application Ser. No. 10/270,153 filed on Oct. 15, 2002, now issued U.S. Pat. No. 6,834,932, which is a Continuation of U.S. application Ser. No. 09/575,117 filed on May 23, 2000, now issued U.S. Pat. No. 6,464,332.
FIELD OF THE INVENTION
The present invention relates to the field of ink jet printing and in particular discloses a method and apparatus for the compensation for the time varying nozzle misalignment of a print head assembly having overlapping segments.
CO-PENDING APPLICATIONS
Various methods, systems and apparatus relating to the present invention are disclosed in the following co-pending applications filed by the applicant or assignee of the present invention simultaneously with the present application:
6428133
6526658
6315399
6338548
6540319
6328431
6328425
6991320
6383833
6464332
6390591
7018016
6328417
6322194
6382779
6629745
09/575197
7079712
6825945
09/575165
6813039
6987506
7038797
6980318
6816274
7102772
09/575186
6681045
6728000
7173722
7088459
09/575181
7068382
7062651
6789194
6789191
6644642
6502614
6622999
6669385
6549935
6987573
6727996
6591884
6439706
6760119
09/575198
6290349
6428155
6785016
6870966
6822639
6737591
7055739
7233320
6830196
6832717
6957768
09/575172
7170499
7106888
7123239
6409323
6281912
6604810
6318920
6488422
6795215
7154638
6924907
6712452
6416160
6238043
6958826
6812972
6553459
6967741
6956669
6903766
6804026
7259889
6975429
The disclosures of these co-pending applications are incorporated herein by cross-reference.
BACKGROUND OF THE INVENTION
In the applicant's co-pending application PCT/AU98/00550, a series of ink jet printing arrangements were proposed for printing at high speeds across a page width employing novel ink ejection mechanisms. The disclosed arrangements utilized a thermal bend actuator built as part of a monolithic structure.
In such arrangements, it is desirable to form larger arrays of ink ejection nozzles so as to provide for a page width drop on demand print head. Desirably, a very high resolution of droplet size is required. For example, common competitive printing systems such as offset printing allow for resolutions of one thousand six hundred dots per inch (1600 dpi). Hence, by way of example, for an A4 page print head which is eight inches wide, to print at that resolution would require the equivalent of around 12800 ink ejection nozzles for each colour. Assuming a standard four colour process, this equates to approximately fifty one thousand ink ejection nozzles. For a six colour process including the standard four colours plus a fixative and an IR ink this results in 76800 ink ejection nozzles. Unfortunately, it is impractical to make large monolithic print heads from a contiguous segment of substrate such as a silicon wafer substrate. This is primarily a result of the substantial reduction in yield with increasing size of construction. The problem of yield is a well studied problem in the semi-conductor industry and the manufacture of ink jet devices often utilizes semi-conductor or analogous semi-conductor processing techniques. In particular, the field is generally known as Micro Electro Mechanical Systems (MEMS). A survey on the MEMS field is made in the December 1998 IEEE Spectrum article by S Tom Picraux and Paul J McWhorter entitled “The Broad Sweep of Integrated Micro Systems”.
One solution to the problem of maintaining high yields is to manufacture a lengthy print head in a number of segments and to abut or overlap the segments together. Unfortunately, the extremely high pitch of ink ejection nozzles required for a print head device means that the spacing between adjacent print head segments must be extremely accurately controlled even in the presence of thermal cycling under normal operational conditions. For example, to provide a resolution of one thousand six hundred dots per inch a nozzle to nozzle separation of about sixteen microns is required.
Ambient conditions and the operational environment of a print head may result in thermal cycling of the print head in the overlap region resulting in expansion and contraction of the overlap between adjacent print head segments which may in turn lead to the production of artifacts in the resultant output image. For example, the temperature of the print head may rise 25° C. above ambient when in operation. The assembly of the print head may also be made of materials having different thermal characteristics to the print head segments resulting in a differential thermal expansion between these components. The silicon substrate may be packaged in elastomer for which the respective thermal expansion coefficients are 2.6×10 −6 and 20×10 −6 microns per degree Celsius.
Artifacts are produced due to the limited resolution of the print head to represent a continuous tone image in a binary form and the ability of the human eye to detect 0.5% differences in colour of adjacent dots in an image.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide for a mechanism for compensating for relative displacement of overlapping print head segments during operation in an effective and convenient manner.
In accordance with a first aspect of the invention there is provided in an ink ejection print head comprising a plurality of overlapping print head segments, wherein the spatial relationship between adjacent segments is variable with time, a method for controlling the firing of nozzles within the overlapped segments comprising the steps of: (a) determining a measure of the overlap between adjacent print head segments; (b) creating a half toning pattern for the nozzles in the region of overlap of the overlapping segments; and (c) adjusting said half toning pattern as a function of said measure in the overlapping regions of said print head segments to reduce artifacts produced by the overlapping of said print head segments.
Preferably, the step for determining a measure of overlap employs a measure of temperature of the print head segments The half toning patterns are preferably produced by means of a dither matrix or dither volume and the alteration can comprise adding an overlap value to a current continuous tone pixel output value before utilizing the dither matrix or dither volume. In place of a measure of temperature a measure of distance can be provided by the use of fiduciary strips on each of the segments and using an interferometric technique to determine the degree of relative movement between the segments.
In accordance with a further aspect of the present invention, there is provided an ink ejection print head system comprising: a plurality of spaced apart spatially overlapping print head segments; at least one means for measurement of the degree of overlap between adjacent print head segments; means for providing a half toning of a continuous tone image and means for adjusting said half toning means in a region of overlap between adjacent print head segments to reduce artifacts between said adjacent segments.
The means for adjusting the half toning means can include a continuous tone input, a spatial overlap input and a binary input, the half toning means utilizing the spatial overlap input to vary the continuous tone input to produce a varied continuous tone input for utilization in a look-up table of a dither matrix or dither volume so as to produce output binary values to adjust for the regions of overlap of print head segments. The means for adjusting the half tone or dither matrix may be implemented in hardware or by means of software employing an algorithm.
BRIEF DESCRIPTION OF THE DRAWINGS
This invention is pointed out with particularity in the appended claims. The above and further advantages of this invention may be better understood by referring to the following description taken in conjunction with the accompanying drawings, in which:
FIG. 1 shows a schematic of a pair of adjacent print head segments according to the invention;
FIG. 2 illustrates the process for printing dots from adjacent print head segments as shown in FIG. 1 ;
FIG. 3 illustrates a process of blending dots between adjacent print head segments according to the invention;
FIG. 4 illustrates a process of dither matrix variational control according to an embodiment of the invention;
FIG. 5 illustrates a process of dither matrix variational control according to another embodiment of the invention; and
FIG. 6 illustrates graphically an algorithm implementing a further process of dither matrix variational control according to a further embodiment of the invention.
FIG. 7 shows a schematic of a pair of adjacent printhead segments according to a further embodiment of the invention.
DETAILED DESCRIPTION OF THE EMBODIMENTS
In a first embodiment, a method of compensation for the temperature varying relative displacement of adjacent print head segments is provided by the utilization of a digital processing mechanism which adjusts for the overlap between adjacent segments.
In a print head covering an A4 page width there may be 10 segments having 9 overlapping portions arranged in a repeating sequence of staggered pairs. Initial alignment of segments can be made within 10 microns using techniques well known in the art of monolithic fabrication techniques. The width of a segment for a 6 colour ink arrangement would be approximately 225 microns assuming the nozzles of a segment are arranged on 16 micron centres in a zig-zag pattern longitudinally.
In this embodiment, a temperature sensor is placed on each print head segment so as to provide for a measure of the current temperature characteristics of each print head segment. The current temperature measurement can then be utilized to determine the amount of overlap between adjacent print head segments.
Alternatively, only a single temperature sensor can be used if it can be assumed that the segments of the print head are sufficiently similar to one another in physical characteristics and performance and that the ambient milieu of each pair of overlapped segment is substantially the same.
The degree of overlap is then used to provide a mechanism for controlling the half toning between adjacent print head segments. It is assumed that outputting of an image in the instant invention is by means of digital half toning employing any method or technique well known in the art. Many different half toning techniques can be utilized and reference is made to the text by Ulichney entitled “Digital Half Toning” published by MIT Press.
As shown in FIG. 1 adjacent print head segments 2 , 3 overlap in the respective regions 12 , 13 . The overlap region may extend approximately 40 thou (˜1 mm.) providing an overlap of 64 nozzles spaced at 16 microns for 1600 dpi resolution.
A temperature sensor 16 is placed on each print head segment 2 , 3 so as to provide for a measure of the current temperature characteristics of each print head segment 2 , 3 . The current temperature measurement can then be utilized to determine the amount of overlap between adjacent print head segments. Alternatively, fiduciary strips 100 , 101 on each overlapped segment 102 , 103 , as shown in FIG. 7 , may be used to measure the degree of relative displacement of the segments 102 , 103 by an interferometric technique.
In the region 10 of the segment 2 the nozzles of this segment are used exclusively for the ejection of ink. Similarly in the region 11 of the segment 3 the nozzles of this segment are used exclusively for the ejection of ink. In the overlapping regions 12 , 13 a “blend” is provided between the two print head segments 2 , 3 such that along the edge 14 of the print head segment 2 nozzles are used exclusively in the region 12 to print and similarly along the edge 15 , the nozzles of the segment 3 are used almost exclusively for printing. In between, an interpolation, which can be linear or otherwise, is provided between these two extreme positions. Hence, as shown in FIG. 2 , when printing a full colour output on a page the area on the side 17 is printed exclusively by the print head segment 10 while the area 18 is printed exclusively by the print head segment 11 (as illustrated by the black dots) with the area 19 comprising a blend between the nozzles of the two segments. The printing process utilizes any well known half toning matrix such as disclosed in the aforementioned references. While a known half toning matrix is utilized, the actual print head segment utilized will depend upon the blending ratio provided by the measure of overlap between the overlapping segments.
One such method is illustrated in FIG. 3 where a linear interpolation within the overlapped regions is shown. In the region corresponding to the overlapped section 12 at the edge 14 there is 100% utilization of the nozzles of print head segment 2 , whereas in the equivalent region, edge 7 , of the print head segment 3 there is zero output. As the distance of the overlap region from the line 14 of the segment 2 is increased towards the line 15 of the segment 3 the proportion of utilization of the nozzles of the section 12 is gradually decreased (linearly), being zero at edge 9 while the utilization of the nozzles of the section 13 is progressively increased to unity by the time the edge 15 is reached. In a first embodiment, where there is an increased overlap between nozzles, the half toning thresholds utilized are increased in the overlap region. This reduces the number of dots printed in the blend region. Conversely, if there is a reduced overlap with the print head segments being spaced apart slightly more than normally acceptable, the dot frequency can be increased by reducing the half toning threshold.
An overall general half toning arrangement can be provided as shown in FIG. 4 with a dither matrix 25 outputting a current dither value 26 to a summation means 27 with summation means 27 having another input 28 , an overlap signal, which varies in either a positive or a negative sense depending on the degree of overlap between the adjacent segments. The output value 29 of summation means or adder 27 is compared to the input continuous tone data 32 via a comparator 30 so as to output half tone data 31 . An alternative arrangement allows that the data value 28 can be subtracted from the continuous tone data 29 before dithering is applied producing similar results. This arrangement is shown in FIG. 5 .
As shown in FIG. 5 , a halftone data output 52 can be generated by combining the output 42 of dither matrix 40 in an adder 46 with the overlap signal 44 , and then taking the difference of the output 54 of adder 46 and the continuous tone data 48 in subtracter 50 . This is an equivalent arrangement to that of FIG. 4 .
Through the utilization of an arrangement such as described above with respect to FIGS. 3 and 4 , a degree of control of the overlap blending can be provided so as to reduce the production of streak artifacts between adjacent print head segments.
As each overlap signal 28 can be multiplied by a calibration factor and added to a calibration offset factor, the degree of accuracy of placement of adjacent print head segments can also be dramatically reduced. Hence, adjacent print head segments can be roughly aligned during manufacture with one another. Test patterns can then be printed out at known temperatures to determine the degree of overlap between nozzles of adjacent segments. Once a degree of overlap has been determined for a particular temperature range a series of corresponding values can be written to a programmable ROM storage device so as to provide full offset values on demand which are individually factored to the print head segment overlap.
A further embodiment of the invention involves the use of a software solution for reducing the production of artifacts between overlapped segments of the print heads. A full software implementation of a dither matrix including the implementation of an algorithm for adjusting variable overlap between print head segments is attached as appendix A. The program is written in the programming language C. The algorithm may be written in some other code mutatis mutandis within the knowledge of a person skilled in the art. The basis of the algorithm is explained as follows.
A dispersed dot stochastic dithering is used to reproduce the continuous tone pixel values using bi-level dots. Dispersed dot dithering reproduces high spatial frequency, that is, image detail, almost to the limits of the dot resolution, while simultaneously reproducing lower spatial frequencies to their full intensity depth when spatially integrated by the eye. A stochastic dither matrix is designed to be free of objectionable low frequency patterns when tiled across the page.
Dot overlap can be modelled using dot gain techniques. Dot gain refers to any increase from the ideal intensity of a pattern of dots to the actual intensity produced when the pattern is printed. In ink jet printing, dot gain is caused mainly by ink bleed. Bleed is itself a function of the characteristics of the ink and the printing medium. Pigmented inks can bleed on the surface but do not diffuse far inside the medium. Dye based inks can diffuse along cellulose fibres inside the medium. Surface coatings can be used to reduce bleed.
Because the effect of dot overlap is sensitive to the distribution of the dots in the same way that dot gain is, it is useful to model the ideal dot as perfectly tiling the page with no overlap. While an actual ink jet dot is approximately round and overlaps its neighbours, the ideal dot can be modelled by a square. The ideal and actual dot shapes thus become dot gain parameters.
Dot gain is an edge effect, that is it is an effect which manifests itself along edges between printed dots and adjacent unprinted areas. Dot gain is proportional to the ratio between the edge links of a dot pattern and the area of the dot pattern. Two techniques for dealing with dot gain are dispersed dot dithering and clustered dot dithering. In dispersed dot dithering the dot is distributed uniformly over an area, for example for a dot of 50% intensity a chequer board pattern is used. In clustered dot dithering the dot is represented with a single central “coloured” area and an “uncoloured” border with the ratio of the area of “coloured” to “uncoloured” equalling the intensity of the dot to be printed. Dispersed dot dithering is therefore more sensitive to dot gain than clustered dot dithering.
Two adjacent print head segments have a number of overlapping nozzles. In general, there will not be perfect registration between corresponding nozzles in adjacent segments. At a local level there can be a misregistration of plus or minus half the nozzle spacing, that is plus or minus about 8 microns at 1600 dpi. At a higher level, the number of overlapping nozzles can actually vary.
The first approach to smoothly blending the output across the overlap bridge and from one segment to the next consists of blending the continuous tone input to the two segments from one to the other across the overlap region. As output proceeds across the overlap region, the second segment receives an increasing proportion of the input continuous tone value and the first segment receives a correspondingly decreasing proportion as described above with respect to FIG. 3 . A linear or higher order interpolation can be used. The dither matrices used to dither the output through the two segments are then registered at the nozzle level.
The first approach has two drawbacks. Firstly, if the dither threshold at a particular dot location is lower than both segments' interpolated continuous tone values then both segments will produce a dot for that location. Since the two dots will overlap, the intensities promised by the two dither matrices will be only partially reproduced, leading to a loss of overall intensity. This can be remedied by ensuring that corresponding nozzles never both produce a dot. This can also be achieved by using the inverse of the dither matrix for alternating segments, or dithering the continuous tone value through a single dither matrix and then assigning the output dot to one or the other nozzle stochastically, according to a probability given by the current interpolation factor.
Secondly, adjacent dots printed by different segments will overlap again leading to a loss of overall intensity.
As shown in FIG. 6 , the value for each overlapped segment is plotted along the horizontal axes 60 , 62 as V A and V B respectively between the values of 0.0 and 1.0. The calculated output 66 is plotted with respect to the vertical axis 64 as a function, I A+B , for values ranging from 0.0 to 1.0. A contour plane 68 shows the resultant values for I A+B =0.5.
FIG. 6 shows the qualitative shape of the three dimensional function linking the two segments' input continuous tone values V A and V B to the observed output intensity I A+B . For the first approach, an input continuous tone value V and an interpolation factor f together yield V A =(1−f)V and V B =fV. The closer the interpolation factor is to 0.5 the greater the difference between the input continuous tone value and the observed output intensity. For V=1.0, this is illustrated in FIG. 6 by the curve 200 on the vertical V A +V B =1.0 plane. By definition this curve lies on the function surface. FIG. 6 indicates that when any kind of mixing occurs, that is 0.0<f<1.0, the output intensity is attenuated, and to achieve the desired output intensity the sum of the two segments' input values must exceed the desired output value, that is V A +V B >V. This forms the basis for the algorithm in appendix A.
The function shows a linear response when only one segment contributes to the output, that is f=0.0 or f=1.0. This assumes of course that the dither matrix includes the effects of dot gain.
The foregoing description has been limited to specific embodiments of this invention. It will be apparent, however, that variations and modifications may be made to the invention, with the attainment of some or all of the advantages of the invention. For example, it will be appreciated that the invention may be embodied in either hardware or software in a suitably programmed digital data processing system, both of which are readily accomplished by those of ordinary skill in the respective arts. Therefore, it is the object of the appended claims to cover all such variations and modifications as come within the true spirit and scope of the invention. | A printhead with a series of overlapping printhead segments, all controlled by a print engine controller that adjusts for the temperature variable overlap between the segments to reduce visually perceptible artefacts. The controller sums a current dither value from a dither matrix with an overlap signal to provide an output value which is then compared in a comparator with an input continuous tone data value providing an output compensated dither value to control nozzles in the overlap region of the segments. Alternatively it uses a software program to provide the compensated dither matrix. A temperature sensor measures the degree of overlap of the segments to generate the overlap signal. The degree of overlap may be determined for various temperatures and stored in a ROM. | 6 |
SUMMARY OF THE INVENTION
The object of this invention is a device and power system to provide more efficient motive power to the wheels of a land vehicle and to do other shaft work by means of converting steam pressure from a boiler directly into hydraulic working fluid pressure for motors, without going through ordinary rotating engines and pumps. The expansion of steam in this power system works against a movable piston, the resistive forces of which are determined by the shape of a cam into which the linear force from the expanding steam is mechanically directed. By means of varying the shape of the mechanical linkage cam, the performance of the steam expander can be varied.
In ordinary steam engines, it is necessary to connect the piston to a crankshaft and flywheel and to transmit power by means of gears, shafts, pulleys, etc. On the other hand, a powered piston such as a steam or gas driven one connected directly to a second pumping piston would be limited to pumping fluid at some pressure proportional to the decreasing driving media (steam or gas) as it expands and loses pressure. Such an arrangement would not be very efficient or useful. This invention balances the driving and driven fluid pressures by means of a specific mechanical linkage whose mechanical advantage ratio is programmed to suit the pressure curve of the expanding driving gas.
In a preferred embodiment of the invention, hydraulic fluid, pressurized by small cylinders, working off the transferring cam, is fed directly to one or more hydraulic motors through a system of valves and controls arranged to conserve the energy supplied. Energy is conserved when the vehicle is slowing down, because during that time the hydraulic motor is, by the arrangement of valves, made to transfer the kinetic energy of the moving vehicle back into a pressure accumulator to be used later to propel the vehicle.
Energy is directed to the hydraulic motor and in turn to the driving wheels of the vehicle by valving pressurized hydraulic fluid from an accumulator. The steam expander works on demand from the pressure accumulator and is not connected directly to the driving motor. The vehicle coasting energy is also channeled into the accumulator by way of the hydraulic motor itself. The control of driving power is smooth and highly variable at the operator's demand, being capable of exerting horsepower outputs for short periods of time well above the peak horsepower rating of the prime mover itself.
BRIEF DESCRIPTION OF THE DRAWINGS
A description of this invention will be made using reference to the drawings attached, which are a part hereof.
FIG. 1 is a semi-schematic view of a power plant using the steam hydraulic expander and showing valving and control system to transmit power from heat energy to the rotating motor.
FIG. 2 is a pictorial skeleton view of the various components arranged in a land vehicle in a fashion to propel it.
FIG. 3 shows a schematic example of the method of transfer cam design to effect a constant hydraulic pressure under conditions of decaying steam pressure as encountered in operation of the device shown in FIG. 1.
FIG. 4 shows a table with cam positions a, b and c as shown in FIG. 3.
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIG. 1, combustible fuel such as alcohol, oil or butane gas is fed from container 1 to burner 2 and is burned to convert water to steam under pressure in boiler 3. A preset steam pressure in the boiler such as 300 psi, 500 psi, or more is maintained by the feedback control comprised of the pressure transducer 4, impulse tube 5 and valve 6, in the usual manner, by which increased pressure, for example, in the boiler is sensed by the transducer and a valve closing impulse is transmitted to valve 6 reducing the rate of burning in burner 2, thereby tending to lower and hence maintain a constant pressure in the boiler.
Steam from the boiler is throttled through valve 7 to the inlet manifold 8 of the steam expander 9.
When valve slide 10 is in the position shown, to the right in FIG. 1, which is the inlet position for the right cylinder chamber 11, steam enters through port 12 and expands against piston 13, drawing transfer cam 14 to the left by action through piston rod 15. This motion forces piston 16 in hydraulic cylinder 17 upward, in the drawing, by bringing surface 18 of cam 14 to bear against cam roll follower 19, thereby pushing piston rod 20 upward. As piston 16 moves upward, hydraulic fluid in cylinder 17 is forced under pressure through check valve 21 into accumulator 22. Accumulator 22 can be an air over oil type, springloaded, diaphram, or nondiaphram.
The ratio of area of the steam piston 13 to the smaller hydraulic piston 16 is of the order of 5 to 1. Further, the mechanical leverage, or mechanical advantage, of cam 14 and follower 19 is on the order of 2 to 1, rod 20 moving approximately half the distance of rod 15. The combination of these two force ratios make possible very high hydraulic pressures in accumulator 22 as compared to steam pressure in boiler 3. But more importantly to the novel feature of this invention is the fact that the force ratio between 15 and rod 20 is different in different parts of the stroke. This is made possible by the contour of cam face 18 which becomes less steep as piston 13 progresses toward the left in FIG. 1 and toward the end of its leftward stroke.
Consider at this point that valves 23 and 24 are closed so that the system is in a mode building up hydraulic pressure in accumulator 22. This mode is chosen at this point in the description so as to completely describe the novel thermodynamic effect before proceeding on from the accumulator to the remainder of the power system. The steam expander 9 is shown with valve operating slides 10 for inlet and 25 for outlet. Yoke 29 causes pin 31 to move back and forth in slot 30 in slide 10. Slot 30 is slightly shorter than 1/2 stroke length, therefore yoke 29 and piston 13 move some distance before slide 10 is moved at either end of the stroke. The above described device allows inlet valve 32 to close when the piston 13 is only partway into its power stroke. This early closing of steam inlet is known as "cut-off" and will be referred to later in a description of efficiency.
Outlet valve slide 25 is also caused to move slightly at each end of the piston 13 stroke by means of pin 36 in slot 37. Slot 37 is slightly shorter than a full piston stroke length. Pin 36 is attached to yoke 29 and moves back and forth with the piston 13. The varying sequence is the same as for ordinary steam engines and is as follows:
1. Piston moving from right limit to mid
inlet 32 open
inlet 33 closed
outlet 34 open
outlet 35 closed
2. Piston moving from mid to left limit
inlet 32 closed
inlet 33 closed
outlet 34 open
outlet 35 closed
3. Piston moving from left limit to mid
inlet 32 closed
inlet 33 open
outlet 34 closed
outlet 35 open
4. Piston moving from mid to right limit
inlet 32 closed
inlet 33 closed
outlet 34 closed
outlet 35 open
This type valving will operate as shown but it is to be understood that any system of valving such as external from mechanical linkage, or limit switch solenoid valves, arranged to alternately admit live steam and exhaust spent steam to ports 12 and 26 and from ports 27 and 28 to cause piston 13 to reciprocate, would suffice. The valve slide 10 has dimensions such that steam is admitted to the cylinder chambers 11 and 38 alternately only while the piston 13 is near one of the ends and only for a short distance of its power travel. The steam inlet is then cut off by the inlet valve which is the ordinary method for steam engines. After this "cut off" point, the steam expands adiabatically, changing its thermal energy into mechanical energy in moving the piston. The steam, in so doing, decreases in temperature and decreases in pressure. To accomodate this decrease in pressure against the top area of the steam piston 13 and maintain the same hydraulic pressure on hydraulic piston 16, the mechanical advantage of the linking mechanism must be changed. This change in mechanical advantage is brought about by the fact that the cam face angle 18 changes over its length. For example, if at the beginning of the steam piston stroke the steam pressure is 400 psi and the cam face is angled to provide a 2 to 1 mechanical ratio between forces on shaft 15 to shaft 20, and if steam piston 13 area to hydraulic piston 16 area are in the ratio of 5 to 1, then the hydraulic pressure in cylinder 17 will be
2×5×400=4,000 psi.
In this example, when the steam piston then moves in the cylinder to a place where the expanding steam pressure has decreased from 400 psi to 200 psi, the corresponding position of follower 19 cam face 18, will be in a region where the cam face angle is shaped such to effect a 4 to 1 mechanical advantage. The hydraulic pressure at this latter point of travel in the example will be
4×5×200=4,000 psi.
In this manner, the hydraulic pressure is maintained at 4,000 psi flowing out of cylinder 17, even though the steam pressure in cylinder 11 is decreasing, as it must do to give up its thermal energy efficiently.
To utilize the energy in the form of flowing, high pressure, hydraulic fluid issuing from cylinder 17 as described above, a continuous system of refilling cylinder 17 with low pressure working fluid to be pumped in turn at high pressure, and a hydraulic motor with necessary controls is provided. High pressure hydraulic fluid passes from cylinder 17 through the pass direction of check valve 21 and into pressure accumulator 22. To cause hydraulic motor 39 to rotate, throttle valve 23 is opened by hand, or foot, on demand. Working fluid cannot flow out of accumulator 22 through check valve 40 because of check valve's 40 directionality. Working fluid flows through motor 39 and through valve 24 which is also opened simultaneously with valve 23 because both valves are mechanically tied together such as by having a common operating shaft. The fluid does not at this time go through check valve 41, even though the direction is right, because the spring loaded check opening ball is set at a pressure higher than is in cooler 44 and low pressure accumulator 43. In other words, check valve's 41 crack pressure is set at about 4,200 psi. The fluid, therefore, flows into cooling coil 44. Out of cooling coil 44 the fluid does not flow through check valve 45, because its opening spring is set at a pressure higher than exists in low pressure accumulator 43. The fluid then flows into and past accumulator 43 at a low pressure and on through check valve 46 and into cylinder 49. Fluid does not flow from accumulator 43 through either check valve 47 or check valve 48 because pressure on the arrow side of these valves is higher than in accumulator 43 and the valves are held closed by that pressure. At this time, piston 50 is moving up in cylinder 49 because piston 13 and cam 14 are moving to the left in FIG. 1. Cylinder 49 is thus being filled with low pressure fluid. In brief summary of this much of the operation, piston 16 is pumping fluid through motor 39 causing the motor to do shaft work and the fluid is continuing on under a lowered pressure to fill cylinder 49 to make it ready to do the same when the steam piston 13 is on its left to right stroke. Piston 50 moves up as steam piston 13 moves right to left because cam face 51 is shaped to allow cam follower 52 to move up as low pressure fluid pushes against piston 50.
As steam piston 13 moves to the left in expander cylinder 9, spent steam in cylinder volume 38 is forced out through port 27, into outlet manifold 52 and into condenser 53. The condensed exit steam is pumped as a liquid by pump 54 back into boiler 3.
When steam piston 13 arrives at the leftward position in expander cylinder 9, inlet valve 33 opens port 26 because slide 10 has moved to a position causing the protrusion shown to push valve 33. At this new leftward position of valve slide 10 (this position not shown in FIG. 1) steam from boiler 3 enters port 26 and pressurizes the left cavity 38 of cylinder 9. Piston 13 then moves in a rightward direction as the steam expands in cavity 38. Piston rod 15 then pushes cam 14 from its then leftward position (not shown) to the right. During this left-to-right stroke piston 50 is forced downward in cylinder 49 in the same manner as piston 16 was forced upward in cylinder 17 during the stroke in the other direction as described before. When the steam piston first starts its left-to right stroke, piston 16 starts down and hydraulic pressure in cylinder 17 drops off in intensity rapidly. This drop in pressure in cylinder 17 causes check valve 21 to close, because back pressure from accumulator 22 overcomes it. Thus accumulator 22 does not lose pressure back to cylinder 17. Meanwhile, still during the left-to-right stroke of steam piston 13 and simultaneous downward stroke of piston 50, high pressure fluid from cylinder 49 flows through check valve 47 and into accumulator 22 and on to the motor 39, if valve 23 is still held open by the operator. This time it is cylinder 17 which is being filled with low pressure fluid from accumulator 43 flowing through check valve 48 but not through check valve 46 or 21 because this return fluid's pressure is too low to open check valves 46 and 21 against the high pressure on the other side. Nor does this low pressure working fluid pass through check valve 45 because of the higher pressure on its outlet side.
In the mode of operation, two strokes of which were described above, when "motor-operate" valves 23 and 24 are held open and the motor 39 caused to run, piston 13 will continue to reciprocate drawing steam from boiler 3 and alternately pressurizing fluid in first cylinder 17, then 49 and thus maintaining pressure in accumulator 22, even though fluid flows through motor 39. A pressure sensor 54 in accumulator 22 is connected to impulse line 55 which is connected to steam valve 7. The pressure sensor 54 is preset at a desired hydraulic fluid working pressure, say 4,000 psi. Sensor 54, impulse line 55 and valve 7 work in the normal feed back loop control action so that as motor demand of fluid out of accumulator 22 lowers accumulator 22 pressure, below say 4,000 psi, valve 7 opens more, throttling more steam to expander 9 and causing hydraulic cylinders 17 and 49 to deliver more hydraulic fluid to accumulator 22. Conversely, when pressure in accumulator 22 exceeds its set point, of say 4,000 psi, by a small amount, such as is caused by the operator closing or partially closing valves 23/24, an impulse in line 55 causes steam valve 7 to be closed and the reciprocating action of piston 13 slows or stops.
Upon restart of the steam piston, as when pressure in accumulator 22 is lowered and valve 7 opens, it may be that piston 13 is positioned in its stroke with both inlet valves 32 and 33 closed. In this case in order to start the action, steam from line 56 will enter one or the other ends of expander 9 by passing through either valve 57 or 58 depending on the direction piston 13 was last moving. Exist valve slide 25 moves, as was described above, a small amount left and then right as piston 13 reaches each end of its stroke and upon this movement valves 57 and 58 are either held open or allowed to remain normally closed alternately. In FIG. 1, valve 57 is open and steam enters the small port shown in chamber 11. It can be seen from FIG. 1 that steam flows into either chamber 11 or 38 only when piston 13 is on a power stroke using that side of the piston. The amount of steam entering through valve 57 (or 58 in its turn) is relatively small compared to the amount entering through ports 12 (and 26) and is mainly to slowly start a stopped piston upon start-up. The steam that does enter through bleed valves 57 and 58 does work during the power strokes and is never wasted.
Next will be described the mode of operation in which the kinetic energy of a coasting down but moving vehicle in which the present power system is installed, is converted back into stored energy in the system shown in FIG. 1. In this mode of operation, the operator of the vehicle has closed valves 23 and 24, preventing any further flow of working fluid from the high pressure accumulator 22 and preventing any further flow of working fluid to low pressure accumulator 43. Note that in this mode, valve 7 will close and in turn valve 6 will close, because both steam pressure at 4 and hydraulic pressure at 54 will quickly reach cut off set point of the controls as described previously. Therefore, no further usage of fuel and no motion of the expander will take place.
In the above slowing down mode, hydraulic motor 39 will be driven by the turning wheel or wheels of the vehicle and act as a pump. The pump action of 39 forces working fluid through check valve 40 into accumulator 22. Check valve 40 is spring loaded to open in the direction indicated when the pressure on its inlet exceeds the pressure on its outlet side. The motor 39, acting as a pump, is capable of delivering fluid at a pressure considerably in excess of previous accumulator 22. For example, if working fluid pressure in accumulator 22 has been set at 4,000 psi, motor 39, when powerfully driven through its shaft as a pump, will develop outlet pressures of 5,000 psi. As the motor 39 runs as a pump, hydraulic fluid enters the top line of the motor from accumulator 43 by flowing through check valve 45. This mode of operation is now pumping working fluid from accumulator 43 at a low pressure into accumulator 22 at a high pressure thereby storing energy for use later as demanded by operator. The capacity of accumulators 43 and 22 are approximately equal in volume of fluid capable of being held therein. When the present invention is to be used in the energy recovery from a coasting down vehicle mode, as is being described, the size of accumulators 22 and 43 are large enough to store enough energy to later accelerate the vehicle to 20 or 30 miles per hour. This volume is from one to several cubic feet at 2,000 psi to 5,000 psi.
During energy recovery coasting mode it frequently occurs that accumulator 22 reaches its highest limiting pressure and can hold no more fluid. A preselected pressure of, for example, 1,000 psi over accumulator's 22's normal working pressure, described earlier in the working mode, is selected as a highest limit for accumulator 22. Check valve 41 has been previously set by its spring load to open at this preselected pressure, for example, 5,000 psi. When this pressure is reached and motor 39 continues to operate as a pump, being driven as it is from the propelling wheels of the coasting vehicle to which it is connected, working fluid will then circulate through check valve 41, cooling coil 42 and motor 39.
If vehicle, wheels and motor 39 come to a stop, a static pressure of the preset value, mentioned above, will be maintained in accumulator 22, in lines connecting valve 40 to valve 41, in the motor 39, and in lines connecting 45 to valve 41 by way of cooling coil 42.
Returning now to the power demand mode, the operator opens valve 23 and 24 simultaneously allowing high pressure fluid from accumulator 22 to drive motor 39. Only after pressure in accumulator 22 had been depleted to an intensity below transducer 54 set point, will valve 7 open and start expander piston 13 in motion. This period of time, when the stored pressure in accumulator 22 which may be, for example, 5,000 psi, is decreasing to a pressure equal to transducer 54 set point, for example, 4,000 psi, is enough to return the stored energy, built up from the coasting mode to the motor, and accelerate the vehicle into motion without calling on boiler 3 to deliver any energy. Eventually, valve 7 does open and the system returns to the power mode described previously.
The components of this power system can be, in one embodiment of this invention, arranged in a land vehicle, as shown in FIG. 2. In FIG. 2 air to fluid heat exchanger 3 is located as shown at the front of the vehicle. Beside this heat exchanger is steam condenser 4 located where it can receive a flow of air for cooling purposes. Boiler 2, with its burner underneath, is shown also near the front of the vehicle and under its fuel tank 1. Expander 5 and associated mechanical linkage to hydraulic motors, 8 and 9, are shown shafted on each to the rear wheels, 10. Accumulators 6 and 7 are shown as cylindrical containers lying flat at the frame level of the vehicle. Exact valving and connecting lines, used in FIG. 1, are not shown in FIG. 2. In FIG. 2, element 11 illustrates a valve or control element in the lines.
In a vehicle, utilizing the power plant of this invention, the auxiliary power needs such as electric generator for battery and lights, cooling fans, pumps, etc, are driven by small hydraulic motors feeding off of the main accumulator 7 in FIG. 2.
The method of contouring cam 14 of FIGS. 3-4 is best described by reference to FIG. 3. It is seen in FIG. 3 that the tangent angle of the cam at the follower contact point is higher at position a than b, and higher at b than at c. As the steam piston moves to the right in FIG. 3 the steam pressure P s decreases ideally according to the gas law PV=C, where P is pressure, V is volume and C is the gas constant. However, since the expansion of the steam is not ideal due to deviation from adiabatic conditions necessary in a practical situation, the actual pressure-volume diagram is obtained by instrumentation of the cylinder in the usual manner such as by a steam indicator or by pressure transducers and linear displacement transducers feeding an YX recorder.
Having determined the steam pressure at various positions of the steam piston, the corresponding steepness of the cam at those positions necessary to maintain a constant hydraulic pressure in a cylinder whose piston is driven by the cam follower is determined by the following formula:
θ=arc tan (A.sub.s P.sub.s)/(A.sub.h P.sub.h)
in which θ is the angle of a tangent line drawn at the cam follower contact point as shown in FIG. 3.
A s is the area of the steam piston.
P s is the steam pressure at the position in question.
A h is the area of the hydraulic piston driven by the cam.
P h is the desired constant hydraulic pressure to be pumped.
The table shown in FIG. 4 illustrates the use of the formula for three points on the cam corresponding roughly to the beginning (a), middle (b), and end (c) of a steam expansion stroke. An area of 5 square inches has been selected in this example as the size of the steam piston, an area of 1 square inch has been selected as the size of the hydraulic piston and a constant hydraulic pressure of 3,000 psi has been selected. A starting steam pressure of 300 psi has been selected and it has been assumed that at position b the steam pressure has fallen to 210 psi and that at position c the steam pressure has further expanded to 95 psi. Using the formula
θ=arc tan (A.sub.s P.sub.s)/(A.sub.h P.sub.h)
to work across the table, the method gives cam angles of 26.6°, 19.3°, and 10.8° respectively for points a, b and c on the cam. When contouring a complete cam for use in this invention a large number of such position points is selected and a table as shown in FIG. 4 is worked out containing as many as one point for each one-eighth inch of cam travel, thereby when physically contoured from steel or hard metal a smooth curve is approximated for the cam follower to ride on. | A method of converting steam pressure from a boiler into a constant pressure hydraulic fluid working media and system for efficiently utilizing the hydraulically stored energy in a land vehicle or the like. A reciprocating steam piston actuates one or more hydraulic pistons in cylinders without going through a crankshaft or other rotating parts. A means of recuperating kinetic energy from a decelerating vehicle and storing it as pressurized working fluid is provided. | 5 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This utility patent application is a divisional of pending U.S. Utility patent application Ser. No. 10/687,159, having a filing date of Oct. 16, 2003, which claims the benefit of U.S. Provisional Patent Application Ser. No. 60/418,834, filed Oct. 16, 2002, now abandoned, entitled “Method for Preparing an Ion Exchange Media,” having named applicants as inventors, namely Ravi Chidambaran, Pavan Raina, and Devesh Sharma. The entire contents of U.S. Provisional Patent Application Ser. No. 60/418,834 and U.S. Utility patent application Ser. No. 10/687,159 are hereby incorporated by reference into this utility patent application.
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 REFERENCE TO A “MICROFICHE APPENDIX”
[0004] Not Applicable.
BACKGROUND OF THE INVENTION
[0000] Field of the Invention
[0005] The subject invention relates to a method for preparing a composite ion exchange media for use within an electro-deionization process. This invention effectively differentiates the role of the media within the dilute compartment and describes a new method of preparation, which is able to meet the intended roles and enhance the performance.
[0006] It has been found that the media performs multiple functions involved within the dilute stream chamber. For example: ion exchange, transport of de-ionized ions collected in the dilute compartment to the concentrate the compartment. These steps have to happen at a particular rate and the kinetics are defined by the flow of water through the system and the ionic load transferred by the influent. While the flow is limited by the pressure drop through the system the ionic load is limited by the ability of the system to transport the load into the concentrate compartment and stay regenerated so that quality of water at sustained levels can be produced consistently. For each function (flow and transport) there is an optimum configuration, form, and method of preparation which cannot be achieved if there is a uniform design. If the design is uniform for the whole mass of the media, it will only perform one of the functions efficiently whereas performance on other functions will be less than optimum.
[0007] This invention involves detailed study on the mechanisms for these functions in a stepwise manner and limitations involved therein. Work has also been done to overcome the limitations through an effective combination of a media configuration, which allows handling of these functions by segregating the requirements and making them happen in an efficient manner in specific zones.
BRIEF SUMMARY OF THE INVENTION
[0008] The ion exchange media in the dilute compartment of an electro de-ionization process is required to fulfill the following two requirements.
1. Effectively exchange the ionic load being fed in through the feed water to be de-ionized; and 2. Transport the ions to the concentrate compartment while remaining in a highly regenerated form.
[0011] It is very clear through several sets of experiments that if the flux has to be maximized the media should be such that it offers minimum resistance to the flow path. However, by doing this there is a limitation in terms of the thickness because of the ability of the system to transfer ions to the concentrate compartment. This can be quickly seen in terms of deteriorating quality that needs flow to be reduced to maintain quality. This also is seen in terms of the number of the hours it takes to get the quality to a target value when the stack is started up or the stack is regenerated after exhaustion during operation.
[0012] At the same time, if the media is made of finer resin particles the ion transportation is significantly improved evidenced by the time taken to get a desirable quality but the flux achieved is not satisfactory.
[0013] Therefore, a media was invented with a combination of the two in an optimum proportion such that the ability of the media to handle flow and transport of ions within itself and through to concentrate does not limit the quality on a sustainable basis.
[0014] The media broadly consists of two parts. The porous part, which is named as Part 1 for ease of description, and the transport framework, which is named Part 2 , for ease of description. There are several objectives to be kept in mind for the porous part of the media, which are as listed below:
A]. Part 1 has to be in a uniformly porous form as possible so that the water flow is possible with maximum flux. This part of the media, if reduced in size, will start offering resistance to the water flow. B]. Part 1 of the composite media should form the bulk of the volume so that opportunity to increase the flow through the system can be maximized. C]. Part 1 also has to stay regenerated so that efficiency of ion transport can be maintained. Therefore, the media has to remain continuously exposed to an environment where regenerating ions are available on a continuous basis. D]. So that the objective mention in C above can be achieved all the bipolar sites have to be created on this path by design. E]. This concept also operates on a basis that water splitting that happens on resin-resin interfaces only creates necessary regenerating ions which are efficiently utilized in the regeneration therefore eliminating any water splitting between resin membrane interfaces by design. F]. The design of this part is done to achieve an objective of equal water distribution across the width of the media by providing flow dividers as a part of the media. Consequently, length covered by water within the media does depend on the location of the water entry within the media or difference in porosity of the media. This is therefore achieved without introduction of an inert material.
[0021] There are several objectives that need to be defined for the transport framework, Part 2 , which are as follows:
A]. The main function of Part 2 of the composite media is to facilitate ion transport into concentrate compartment in a way that ion transfer is efficient into the concentrate compartment. B]. Part 2 , of the media forms a framework around Part 1 of the media, which takes flow. C]. This part of the media does not encourage any flow because of the fine particle size it is made of and compactness of the structure. However the media can get wet and still maintain a highly conductive ion transport environment. D]. The media of Part 2 ensures almost seamless contact with membrane ion-exchange surface on either side and also is in complete contact with the base media, Part 1 . As a result, there is no channeling of water close to the membranes, which is the case in many designs. If this part is made with exhausted resin the chances of any channeling are further eliminated because of swelling of resin with regeneration that further compresses it against the membrane surface.
[0026] The Part 2 media is smooth and soft in texture and therefore almost becomes a part of membrane on one side and an extension of porous media on the other side. This is totally able to eliminate bypassing of water through the boundary layer gaps, when the resin is not fully regenerated.
E]. The media is made to have a very fine surface ensuring complete contact of the membrane and porous media surface so that there are no gaps for ion movement providing for a continuous ion exchange environment within the dilute compartment. F]. While most of the framework is close to the membrane surface, part of this also extends to form flow defining channels for the porous media so that flow path can be maintained through the length of the media without the introduction of an inert media. G] The transport framework being attached to the ion exchange membrane allows the total membrane surface to be used in transport of ions across to the dilute chamber and also eliminates membrane-resin bipolar sites which reduce efficiency of transport. H]. Minimizing and optimizing the bipolar junctions to only resin-resin bipolar surfaces thus reducing power consumption by preventing any undesirable water splitting.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0031] FIG. 1 is a depiction of separate cation and anion resin beds used to form the transport framework of the invention.
[0032] FIG. 2 depicts cation blocks and anion blocks of sizes used in one embodiment of the invention. Unites are millimeters.
[0033] FIG. 3 is an exploded view of composite media created according to the invention. This embodiment displays four flow paths between the anion part of the transport framework and the cation part of the transport framework.
[0034] FIG. 4 is a depiction of a transport framework including four flow paths, each flow path having six cation exchange areas and six anion exchange areas.
[0035] FIG. 5 includes two views of the ion exchange media of the invention.
[0036] FIG. 6 is a graphical representation of product resistivity over time for an electrodeionization stack run without the benefit of the ion exchange media of the instant invention.
[0037] FIG. 7 is a graphical representation of product resistivity over time for an electrodeionization stack including in its dilute compartment the ion exchange media of the invention.
[0038] FIG. 8 is a graphical representation of product resistivity over time for a thirty cell-pair electrodeionization stack including in its dilute compartment the ion exchange media of the invention.
[0039] FIG. 9 presents two views of the flow paths with dividers.
DETAILED DESCRIPTION OF THE INVENTION
[0040] Keeping in mind the abovementioned requirements a media design has been created wherein a media is made with two different kind of resin configurations. An outer two part transport framework is created with fine resin (bound with a cohesive) that is capable of getting wet but is not conducive to water flow through it. However, because of close and compact configuration, it provides an efficient transport route for ions to the concentrate compartment in the direction of the driving force. This transport framework does not allow bypassing of the flow through the boundary layer because the cation and anion part of the framework is in complete contact with the respective like cation or anion membrane.
[0041] For making the framework part of the media, both varieties of resins in regenerated or exhausted form are dried at controlled temperatures and ground to reduce the size between 50-150-micron size. The ground resin is sieved to make sure larger particle size particles are positively removed. This resin is then impregnated into a binding media and it is thoroughly mixed so that it becomes uniformly distributed. It is then allowed to partially dry for sufficient time so that a dough-like mixture can be made.
[0042] Once this mixture becomes dry to an extent of a desirable level of consistency that it can be given any shape or form it is rolled or pressed into the shape of a framework depending on the design and then allowed to dry completely. The thickness of the framework can be adjusted based on the quantity and the size in terms of length and width depending on the size of the dilute compartment. This process is followed for both types of resins for either side of compartment, which is then boxed together if the dividers are made as a part of framework. If the dividers are not a part of the framework, they are internally divided by using separate dividers to create to exact shape of the Flow path zones. These Flow path zones may be called elsewhere as cation or anion zones, blocks, tablets, or domains. These are used to fill up the void spaces within the box. The overall framework is now ready to receive the second part of the media, which makes the flow path in the void space available. This design of the transport framework can be suitably created for different thickness of the dilute compartment ranging up to a thickness 14-mm or even more.
[0043] The preparation of media in the flow path, involves carefully calculating quantities of resin volumes required based on the moisture content of resin and the type of resin for a given particle size based on the bulk densities. The resin utilized, is uniform in size from 500-650 micron, and is used for the part of the media to process the flows. This resin can be bound into a different configuration using a binding agent depending on the shape and size of the longitudinal path created within the Transport framework part of the media. This shape can be based on a square, circular, rectangular or any other cross-section. This is then given the form of flow path domains. The cation and anion domains or blocks for the flow paths are of different size and can be used to fill into the void space in the frameworks in required predetermined quantities. This part of the media can also be made with dry resin, which is in a regenerated or exhausted form. Within the framework predetermined flow paths are created to guide all the flow through defined cross sections in the longitudinal direction with alternative cation and anion resin blocks or tablets. These blocks can be in a square, rectangular, cylindrical or any other geometrical shape, which facilitate ion transfer from water to resin based on the shape of the voids. The cation and anion ratio within the longitudinal flow path is adjusted to achieve the flux and bipolar surface area required, within a defined bed depth. The number of blocks are determined and adjusted based on the bipolar area required. This media is kept in bound form for ease of preparation or even can be used without any binding agent.
[0044] The binding agent can be low-density polyethylene or their mixture, natural rubber, butyl or Nitrile rubber or combinations. However best results are obtained with Nitrile rubber for both the forms of media.
[0045] The packing of tablets into the framework can be done in a horizontal or vertical position depending on which side of the transport framework is kept open. The box is then closed from the open end. For closing the box from the top and bottom polyester or nylon mesh is used. A composite media can be shown as given in FIG. 5 .
[0046] The process of making the composite media can be devised on a manual, semi-automatic or automatic mode.
[0000] Advantages
[0047] This configuration helps in creating a design with efficient features to meet the desired intents at specific places rather than using a design, which is generally made for the overall purpose and creates disadvantages resulting from a lack of control of different steps of the process. The ability of the framework to almost seamlessly combine with both membrane and the porous part of the media is responsible for taking the flow the membranes and media act as one piece. This configuration facilitates achievement of quality immediately after starting the stack in a few hours and also helps in maintaining the quality even if the feed water quality goes through some variation in terms of hardness silica or TOC values. When the resin gets regenerated within the dilute compartment the framework further gets compacted with the membrane largely eliminating possibilities of any by-pass of flow through the membrane surface, which is possible in a conventional media and membrane system. The framework also provides a soft and continuous back up to membranes improving its mechanical strength and longevity and prevents exposure to raw resin surface, which could result in damage to the membrane surface. The process also becomes more resilient to changes in the differential pressures across the dilute and concentrate compartment. Thus the new composite media can be regenerated faster, provide consistent quality of water even with varying feed stock, offers a solution for low levels of silica and improves the mechanical strength and longevity of membranes.
EXAMPLES
[0048] The examples detailed here explain preparation of Flow path domains, blocks or tablets and Transport framework along with flow dividers. These components have been assembled together into a dilute compartment and several of these have been used to create an electro deionization assembly. Various experiments have been carried out and experimental data has been plotted in graphs.
[0049] Method of preparation of media and details of various experiments are as follows:
[0000] Experiment 1 Preparation of the Framework and Tablets
[0050] One set of die is made of the size 200×187 mm of different thickness as required for the selected size of the dilute compartment. The media was made here for dilute compartment thickness of 11.3 mm.
[0051] Anion resin in Cl form and cation in Na form resin separately dried through air or vacuum dried to reduce moisture content between 10 to 20%.
[0052] As shown in FIG. 1 , separate anion resin bed was made by 127 grams on 100% dry basis and blended with suitable binding agent in the range of 1% to 10% (preferably 5 to 7%). The dough was prepared filled in the die and pressed on drying. Similarly separate cation resin bed was by 169 gms of material on 100% dry basis with suitable binding agent in the range of 0.5 to 5%, (preferably between 3 to 5%). The ratio of anion and cation in one bed was kept in ratio of 35% cation and 65% anion and accordingly in the separate anion bed cation blocks that have to be cut and separated out. Under this bed example, the anion blocks size was 47.5×20 mm in the longitudinal direction and cation block size is 47.5×10 mm to give the desired proportion. These blocks are depicted in FIG. 2 . In one bed there are 24 anion and 24 cation blocks. Accordingly from the anion bed separate out 24 blocks of this size and the same number from the cation block to make the bed.
[0053] Intermediate separator or divider: Air or vacuum dried anion and cation resin size was reduced and sieved to collect particle between 50 and 250 μm (preferably around 150 μm). First the sieved resin was blended with 25-50% binding agent and a sheet was prepared of 2-5 mm, preferably 3 mm thick in a die. The dried and pressed sheet was cut to 180 mm length pieces. Such 180 mm pieces were inserted in the cation bed ( 3 a ) and anion bed ( 3 b ) as shown in FIG. 1 and in FIG. 9 .
[0054] Framework preparation, air or vacuum dried, ground and sieved resin of size 50-150 μm was used for the preparation of the framework. This size of resin can also be directly separated out of the resin manufacturing process from its raw materials.
[0055] As shown in FIG. 2 , 17 grams of sized anion on 100% dry basis was taken and blended with 18 to 25% of a binding agent and the dough was rolled to form a layer in the thickness range of 0.5 to 1.0 mm (preferably 0.7 mm). This was allowed to dry and pressed for smoothness. Similarly 22 grams of cation resin material was taken on 100% dry basis and blended with 10 to 20 % binding agent. The dough was rolled similarly as that of anion and pressed on drying to give a smooth surface of thickness between 0.5 to 1.0 mm (preferably, 0.7 mm).
[0056] As shown in FIG. 3 , the anion part of the framework and cation part of the framework were used on either side to create a box with longer dividers on either side of the framework to cover both ends of the length and in between depending on number of flow paths to be created. Alternatively these dividers can be created as a part of each framework directly from the mould. The media made under this example had four equal flow paths created with the help of three dividers of 3 mm each. Polymeric material mesh like nylon is used to cover the top and the bottom ends.
[0057] As shown in FIG. 4 , the basic framework formed was filled in with 24 each of anion and cation blocks or tablets made above. This was then kept under the influence of slight pressure so that it can be all joined together in one piece.
[0058] Six such pieces are prepared for one assembly.
[0059] Assembly: The framework filled bed was placed in the dilute compartment in such a manner that the anion part of the framework is on the anion exchange membrane side and cation portion of framework touches the cation ion exchange membrane. Assembly was then completed with the concentrate compartments and electrodes.
[0060] When the water was passed through the media for wetting the framework that was already an integral part of the remaining bed so that the framework got in close contact with the membrane thus forming a part which remains wet and prevented any chances of water to flow and through close contact with membranes accelerated the ion transfer from the remaining bed towards the membrane and into the concentrate chamber. This assembly was now ready for testing.
[0061] Before the preparation and assembly as above were done a stack was also prepared with six beds of conventional kind of media without the transport framework type beds in order to compare the base level performance with conventional type beds. These stacks had the same dilute compartments same thickness, same ratios of cation to anion resin but the base material was used to fill the thickness. The conventional bed design was based on providing cylindrical cation blocks removed from an anion bed.
[0062] The conventional stack thus operated at 120-150 lts per hour with feed condition of conductivity less than 20 μs/cm, hardness of 1 ppm and later with silica of 200 to 300 ppb. The voltage applied was of 6 to 18 v/p. The product resistivity achieved was 10 to 12 MΩcm and silica less than 20 ppb
[0000] This was observed in 240 hrs of operation
[0063] In the same stack six beds were replaced with the Transport framework and flow path domains type bed as per the method described as part of the invention. The stack was run with increased feed water conductivity as above with hardness of 1 ppm and silica of 200 ppb .The product quality improvement was imminent immediately .The flow through the system increased by 25-30% at a sustained level of quality of 16-18 MΩcm. This configuration continued to perform for more than 500 hrs.
[0064] As seen in FIG. 6 , the stack was run first for 240 hrs with a conventional bed and without the transport framework type bed. The stack stabilization took approximately 40 hours initially to achieve product resistivity of greater than 17.5-18 MΩcm. Silica was then added equivalent to 200 ppb in the feed. Product resistivity started slipping down gradually as shown in FIG. 6 .
[0065] The stack beds were then replaced with frameworks type beds, which are part of the invention. Product resistivity of 18 MΩcm was achieved within 15-20 hours and sustained around that level for next 450 Hrs of operation of this experiment.
[0066] Experiment -2: Thickness of the dilute compartment used was 10.7 mm. Anion resin in Cl form and cation in Na form resin separately air dried to reduce moisture content between 10 to 20%. Separate anion resin bed is made by 125 grams on 100% dry basis and blended with suitable binding agent in the range of 1% to 10% preferably 5 to 7%. The dough is prepared filled in the die and pressed on drying. Similarly separate cation resin bed is by 165 gms of material on 100% dry basis with suitable binding agent in the range of 0.5 to 5% preferably between 3 to 5%. The ratio of anion and cation in one bed was kept the same as experiment-1. The anion and cation blocks were also of the same size. Intermediate separator and the framework preparation were similar as in experiment-1 but adjusted to suit the thickness of dilute compartment.
[0067] All the six beds at this time were having transport framework and flow path domains when the assembly of the stack was done. The stack operated with feed condition of Conductivity of 20 μs/cm, hardness of 1 ppm and silica of 200 ppb. The voltage applied was of 4 and 16 v/p. The product achieved was of 18 MΩcm and silica less than 10 ppb on sustainable basis for more than 500 hrs of operation.
[0068] As seen in the FIG. 7 , this stack was run with the feed of conductivity of 20 μs/cm and silica of 200 ppb. Within first 15 hrs the stack was stabilized and the product resistivity stayed around 18 MΩcm and product silica below 6 ppb through out the run of 700 hrs. This stack feed was also subjected with contamination of TOC between 220 and 440 hrs without the degradation in the product.
[0069] It is also seen in FIG. 7 , there is a dip in the product after 440 hrs, where the bed was exhausted by design to see its ability to regenerate again and give low levels of silica. And it can be seen it was able to regenerate to the original levels of quality of 18 mega ohms within a period of 15-20 hours of operation while continuing to operate with a feedstock of a conductivity of 20 μs/cm. It was also able to deliver silica quality of less than 5 ppb. The assembly was tested for 700 hours.
[0070] Experiment 3: To confirm results on a larger assembly a 30 cell pair stack was made with the media with framework as described above. The RO product was fed to an EDI stack. The assembly was tested for product quality and silica concentration.
[0071] The operating conditions were as follows: Feed flow 1.6 M 3 /hr at 2.5 kg/cm2 pressure, Feed conductivity in the range of 5 to 15 μs/cm, pH of 5.5 to 6.5, Feed silica of 150 to 200 ppb, applied voltage 10 to 15 v/p and ampere consumed 2+/−0.2 amps.
[0072] The product resistivity maintained above 18 MQcm throughout the experiment. The assembly was able to regenerate within 15-20 hours after it was started. The product silica was observed less than 5 ppb with silica going as low as 2 ppb. In the data of 800 hours of operation confirms sustained results. The results are presented in FIG. 8 .
[0073] Obviously, many 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. | This invention presents an ion exchange media including a plurality of cation exchange zones and anion exchange zones in flow paths that are contained in a substantially nonporous resin transport framework. During electrodeionization and other potential applications the ion exchange media of the invention prevents unfavorable water splitting at resin-membrane interfaces and encourages water splitting at resin-resin interfaces where the water splitting may be constructively used to regenerate the resin. | 2 |
BACKGROUND OF THE INVENTION
[0001] The present embodiments relate to bottom injection of cryogen into mixers for cooling and more particularly, to nozzle apparatus that introduce cryogen substances into food products for chilling and/or freezing same, and which apparatus are not clogged from use of the cryogenic substance.
[0002] The bottom injection of cryogen into mixers for cooling food products, for example, are known. Such known bottom injection nozzles for cryogenic substances, such as for example liquid nitrogen (LIN), encounter difficulties when being used with wet products which are drawn into an orifice of the nozzle in communication with the food processing equipment, whereupon the wet food product is frozen upon exposure to the cryogen. When such a situation occurs, the nozzle orifice will become restricted and eventually clogged. Unfortunately, it is extremely difficult to clear the nozzle, frequently requiring disassembly of same, and no further cooling cryogenic substance can be delivered to the mixer for chilling until the clog is removed.
[0003] Existing nozzle structure contributes to this deficiency. That is, known nozzles are made from either thick stainless steel, which transfers a large amount of heat from the mixture or blender wall and thereafter remains cold after an injection cycle of the cryogen until the mixing is complete. This type of stainless steel nozzle contributes to the clogging situation when the cryogenic substance, such as LIN for example, is exposed to the wet product in the blender or mixer.
[0004] Other nozzles are manufactured with a teflon sleeve which reduces the amount of heat transfer from the blender wall to the nozzle, but such nozzles are susceptible to migration of the food product between the sleeve and the housing and will therefore crack the nozzle due to thermal expansion and contraction from the cryogenic substance.
SUMMARY OF THE INVENTION
[0005] There is therefore provided an electrically heated bottom injection nozzle apparatus which consists of a cryogen injection apparatus for injecting a cryogenic substance into a blender, including at least one nozzle constructed for being in fluid communication with an interior of the blender; and an electric heat sink member in contact with the at least one nozzle for electrically heating said nozzle.
[0006] There is also provided herein a method for electrically heating a bottom injection nozzle to eliminate clogging of the nozzle, which includes providing an electric heat sink to said injection nozzle upon conclusion of injecting the cryogenic substance to the blender and transmitting power to the electric heat sink for warming the injection nozzle.
[0007] In summary, the present embodiments include a low thermal mass straight bore nozzle with an integrated heating system which provides for rapid thawing of the nozzle and therefore, clearing of any product within the nozzle between injection cycles of the cryogen, such as liquid nitrogen (LIN). The construction of the nozzle embodiment eliminates the possibility of cracking of the nozzle because there are no internal sleeves used which could permit thermal expansion and contraction of any frozen food product or condensate between the nozzle body and the thermal sleeve.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] For a more complete understanding of the present invention, reference may be had to the following description of exemplary embodiments considered in connection with the accompanying drawing Figures, of which:
[0009] FIG. 1 shows a perspective view of the cryogen injection nozzle embodiment of the present invention; and
[0010] FIG. 2 . shows a side view partially in cross-section of the embodiment of FIG. 1 .
DETAILED DESCRIPTION OF THE INVENTION
[0011] Before explaining the inventive embodiments in detail, it is to be understood that the invention is not limited in its application to the details of construction and arrangement of parts illustrated in the accompanying drawings, since the invention is capable of other embodiments and being practiced or carried out in various ways. Also, it is to be understood that the phraseology or terminology employed herein is for the purpose of description and not of limitation.
[0012] Referring to FIGS. 1-2 , an electrically heated injection nozzle apparatus of the present invention is shown generally at 10 mounted to a wall 12 of a blender or mixer (not shown) in which food product (not shown) is disposed for being chilled. While food product is referred to for being treated by the injection nozzle 10 , it is understood that other types of products can be treated with the present injection nozzle embodiment. The apparatus 10 is shown mounted near or at a bottom region 13 of the blender wall 12 .
[0013] The injection nozzle apparatus 10 or apparatus consists of a nozzle or nozzle portion 14 for introducing a cryogen such as for example LIN represented by the arrow 15 through the nozzle into the blender; a heat sink member 16 ; and an enclosure 18 or housing.
[0014] The nozzle 14 can be either a straight bore stainless steel tube or a machined steel tube with an expanding bore, wherein a diameter of the bore increases along the flow path in the direction of the wall 12 . The nozzle 14 is constructed from a material that has a low thermal mass.
[0015] The heat sink member 16 is used to transfer heat to the blender wall 12 and the nozzle 14 . The heat sink member 16 is constructed with a first heat sink portion 20 for the blender wall and a second heat sink portion 22 for the nozzle 14 . The first and second heat sink portions 20 , 22 may also be formed as an integral unit. The heat sink member 16 is used for transferring heat into the blender wall 12 and to the nozzle 14 . As shown in FIGS. 1-2 , the heat sink member 16 , which includes the first and second heat sink portions 20 , 22 , can be constructed from copper, and the second portion 22 surrounds and is in direct contact with a substantial area of the nozzle 14 . The first heat sink portion 20 is in direct contact with the blender wall 12 .
[0016] Electric cartridge heaters 24 are mounted to or embedded in the heat sink member 16 and connected to a conduit connection 26 at a sidewall of the enclosure 18 . Usually, such sidewall will be at or near a bottom 25 of the enclosure 18 . Electrical connectors 27 interconnect the heat sink member 16 with the conduit connection 26 . The conduit connection 26 is wired to a semi-conductor controlled rectifier (SCR) 28 as shown in FIG. 2 , which conducts the electrical current to the heat sink member 16 . Electric power 30 shown in FIG. 2 is provided to the SCR 28 . A controller or a proportional-integral-derivative controller (PID controller) 32 is connected to the SCR 28 and receives input 34 for defrosting or thawing with the apparatus 10 . That is, the electric cartridge heaters 24 are powered by the SCR 28 and the PID controller 32 , so that the power can be regulated to defrost or thaw the blender wall 12 and the nozzle 14 in a select amount of time. For example, rapid defrost would mean that increased power will be applied to the heat sink member 16 , while a permissible longer duration of defrost will require less power.
[0017] A thermocouple 36 is positioned at an exterior surface of the first heat sink portion 20 as shown in FIG. 2 . The thermocouple 36 can be mounted in a cavity 21 of the portion 20 such that the thermocouple is in facing contact with the wall 12 when the enclosure 18 is mounted to the blender wall. The thermocouple 36 will shut down or stop the defrost operation of the apparatus 10 when a desired set point temperature is reached, which can be for example above 32° F. or 0° C.
[0018] The second heat sink portion 22 is sized and shaped with a bore 40 therethrough which is constructed to receive the nozzle 14 to be extended through the second heat sink portion and the blender wall 12 for opening into the blender. The enclosure 18 is provided with a cylindrical portion 19 extending therefrom and having an open end to which a cap 42 is removably mounted.
[0019] The enclosure 18 or housing is constructed and arranged to protect the nozzle 14 , heat sink member 16 and the electrical cartridge heaters 24 from external impacts and water sprays that may occur in a production facility where the blender is being used. As shown in FIGS. 1-2 , the enclosure 18 includes an internal space 38 or chamber of sufficient volume to support the first and second heat sink portions 20 , 22 , the nozzle 14 , and the electric cartridge heaters 24 therein. The enclosure 18 has a sidewall at least a portion of which is open-sided at 44 , such that the first heat sink portion 20 functions as a sidewall portion for the enclosure. The thermocouple 36 as shown in FIG. 2 is positioned for contacting the wall 12 as discussed above, and covered as well when the enclosure 18 is mounted or seated against the wall shown generally at 44 . The enclosure 18 is contoured so that the sidewall will fit flush with an exterior surface on the blender wall 12 as shown in particular in FIG. 2 An alternate embodiment of the apparatus 10 provides the nozzle 14 , the heat sink member 16 , the enclosure 18 with conduit connection 26 , and the thermocouple 36 as an integral unit.
[0020] The nozzle portion 14 may be constructed from stainless steel; the heat sink member 16 may be constructed from copper or any other highly conductive material, and the enclosure 18 or housing may be constructed from stainless steel or plastic.
[0021] The injection nozzle apparatus 10 of the embodiment showing in FIGS. 1-2 permits the nozzle 14 to be easily cleaned, because the only elements of the nozzle exposed to an interior of the blender is an interior of the nozzle. Therefore, hot water or other cleaning solutions can be sprayed through the nozzle portion 14 for easy cleaning without having to disassemble the injection nozzle 10 .
[0022] In operation with the actual blender (not shown), a batch of food product, such as for example ground meat with ingredients therein, is placed in the blender which is started such that internal blades (not shown) of the blender mix the food product and ingredients. It is required to chill the meat during the blending operation and therefore, cryogen such as liquid nitrogen (LIN) is injected into the blender through the injection nozzle 14 . That is, the LIN 15 is injected through the nozzle 14 during which heat is transferred from the wall 12 via conduction with the nozzle 14 which also has its temperature reduced to a temperature substantially similar to that of the LIN. Minimal heat is transferred between the wall 12 and the nozzle 14 due to a low thermal mass of the nozzle portion. When a desired, reduced temperature of the meat is obtained, injection of the LIN 15 is stopped and the meat is removed from the blender. The controller 32 actuates the SCR 28 for delivering power to the electric cartridge header 24 mounted or imbedded in the heat sink member 16 to warm the first and second heat sink portions 20 , 22 to effectively warm and thaw the blender wall 12 and the nozzle 14 . Any frozen meat or water trapped within and clogging the nozzle portion 14 is warmed and the nozzle 14 can be blown out with a high pressure nitrogen gas prior to the next operating batch being disposed in the blender. The high pressure nitrogen gas will easily discharge any matter from the nozzle into the blender. Since nitrogen is used to dislodge any material in the nozzle 14 , and the next batch will be of similar composition of meat and other ingredients, there is no contamination of the next batch of the product being processed in the blender. The construction of the injection nozzle apparatus 10 permits clean-in-place (CIP) of the nozzle portion 14 without removal or disassembly of the apparatus.
[0023] It will be understood that the embodiments described herein are merely exemplary, and that one skilled in the art may make variations and modifications without departing from the spirit and scope of the invention. All such variations and modifications are intended to be included within the scope of the invention as described and claimed herein. Further, all embodiments disclosed are not necessarily in the alternative, as various embodiments of the invention may be combined to provide the desired result. | A cryogen injection apparatus for injecting a cryogenic substance into a blender, includes at least one nozzle constructed for being in fluid communication with an interior of the blender; and an electric heat sink member in contact with the at least one nozzle for electrically heating said nozzle. A related method is also provided. | 5 |
FIELD OF THE INVENTION
The present invention relates to a shield for a rain water gutter assembly also known as an eaves trough.
BACKGROUND OF THE INVENTION
The use of shields for gutters or eaves troughs is well know in the prior art and many patents have issued for different types of shields. The purpose of the gutter shield is essentially to permit passage of rain water from the roof to the gutter or eaves trough while protecting the same from extraneous foreign matter such as leaves and the like, which could lead to clogging.
In practice, the use of a shield or a guard comprises a member which is apertured and permits the passage of rain water while banning the passage of extraneous material into the gutter. The shields or guards are attached in various manners to a portion to the gutter. However, many of these guards do not function as desired and access must still be had to the eaves trough for cleaning purposes.
It is also been proposed in the art to provide relatively complex structures wherein the eaves troughs are mounted for rotatable movement such that they may be emptied at desired intervals.
It is also being proposed to provide gutters which are designed to have a cover with an outer edge which curls downwardly and the water flow follows the curved portion due to its own surface tension to cascade into the eaves trough which is situated below. All extraneous material would theoretically fall to the ground. However, this concept does not always work when the volume of water becomes sufficiently large so that the surface tension is not sufficient to cause all the water to flow into the gutter. Consequently, there is an overflow.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a novel gutter guard which is securely fixed to the eaves trough on both sides thereof and which forwards the rain water into the gutter, but excludes virtually all foreign matter.
According to one aspect of the present invention, there is provided a device for protecting a gutter wherein the gutter has a rear wall, a front wall and a bottom wall, the walls defining a trough therebetween, the device comprising a guard member having an elongated configuration with a generally planar central portion, first and second longitudinally extending opposed sides located on either side of the generally planar central portion, a plurality of apertures extending through the generally planar central portion, the first side of the guard member having an inverted U-shaped portion designed to fit over an upper marginal edge of the rear wall of the gutter, the U-shaped portion comprising an inner vertical wall and an outer vertical wall, an inturned flange located at the bottom of the outer wall to form a second generally U-shaped portion with the inturned flange being adjacent an inner face of the gutter, the second side of the guard member having an overflow wall extending vertically upward, a generally horizontal portion extending outwardly from an upper end of the overflow wall, and an inturned flange at a distal end of the horizontal portion adjacent the underside of the horizontal portion
According to a further aspect of the present invention, there is provided a device to protect the gutter wherein the gutter has a rear wall, a front wall, and a bottom wall, the walls defining a trough there between, the device comprising a guard member having an elongated configuration with a generally planer central portion, first and second longitudinally extending sides located on either side of the generally planer central portion, a plurality of apertures extending through the generally planer central portion, the first side of the guard member having an upwardly extending wall segment, a U-shaped portion being connected to the upwardly extending wall segment, a flexible sealing member extending outwardly from the U-shaped portion, the second side of the guard member having an overflow wall extending vertically upwardly, a generally horizontal portion extending outwardly from an upper end of the overflow wall, and an inturned flange at the distal end of the horizontal portion, the inturned flange being adjacent to the underside of the horizontal portion.
In a still further aspect of the present invention, there is provided a device to protect the gutter wherein the gutter has a rear wall, a front wall, and a bottom wall, the walls defining a trough there between, the device comprising a guard member having an elongated configuration with a generally planer central portion, first and second longitudinally extending sides located on either side of the generally planer central portion, a plurality of apertures extending through the generally planer central portion, a longitudinally extending flexible sealing member secured to the first of the guard member, the flexible sealing member extending upwardly and outwardly therefrom, the second side of the guard member having an overflow wall extending generally vertically upwardly, and a horizontal portion extending outwardly from an upper end of the overflow wall, the horizontal portion being designed to rest on the gutter.
The device of the present invention provides a guard for the eaves trough to prevent foreign matter from entering into the eaves trough. This is achieved by means of appropriate sizing of the apertures formed therein. In this respect, the aperture size and aperture placement must permit adequate drainage of the water through the apertures into the eaves trough while substantially excluding any foreign matter which remains on the top and which normally would be removed by the element of wind and the like. Adequate sizing of the apertures will prevent clogging of the device.
The apertures preferably extend in diagonal rows or lines at an angle with respect to the gutter length. In preferred embodiments, the apertures have an aperture size of between 2.5 and 10 mm and even more preferably between 3.0 and 4.0 mm. As the apertures are arranged in diagonal rows, they are also preferably arranged in longitudinally extending rows.
In a longitudinally extending row, the apertures are spaced apart by a distance of between 10 and 15 mm while in a diagonal row, they are spaced apart by a distance of between 5 and 10 mm.
As will be appreciated, during a period of heavy rain, the drainage might not be instantaneous and accordingly, there is preferably provided a vertically extending wall adjacent the front wall of the gutter to prevent overflow.
In the first aspect of the invention, there is provided a device which may be supplied in various lengths such that it may be retrofitted to a gutter and/or done by the do-it yourselfer. To this end, there may be provided a connecting member for interconnecting the lengths as they are installed.
In the first embodiment, the device is secured to the gutter by mechanical fastening means while the gutter itself is also secured to the supporting structure by mechanical fastening means such as screws.
In the present invention, the device may be provided with a flexible sealing strip which is retained by the device and is designed above the adjoining structure to prevent water seeping between the gutter and support structure.
BRIEF DESCRIPTION OF THE DRAWINGS
Having thus generally described the invention, reference will be made to the accompanying drawings illustrating an embodiment thereof, in which:
FIG. 1 is a perspective view of a gutter guard and an associated gutter mounted on a supporting structure;
FIG. 2 is a cross-sectional view through the gutter and gutter guard;
FIG. 3 is a detailed sectional view of the upper portion of the gutter guard showing attachment thereof;
FIG. 4 is a cross-sectional view of a further embodiment of the present invention, the view illustrating the gutter guard and means of attachment;
FIG. 5 is a perspective view of the embodiment of FIG. 4 ;
FIG. 6 is a cross-sectional view similar to FIG. 4 showing a modified version of the gutter guard; and
FIG. 7 is a cross-sectional view of a further embodiment of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to the drawings in a greater detail and by reference characters thereto, there is illustrated in FIG. 1 a portion of a gutter generally designated by reference numeral 14 and which is attached to a supporting structure 12 to receive run-off from roof 10 .
Gutter 14 is of a conventional design which is widely available in the market place and has a back wall 16 which is designed to lie substantially adjacent to the supporting structure 12 . Extending between a front row 20 and back wall 16 is a bottom 18 . Front wall 20 includes a lower vertical segment 22 , a central arcuate segment 24 and upper vertical segment 26 . As may be best seen in FIG. 3 , at the upper end of upper vertical segment 26 , there is provided an inwardly extending flange 28 and a reversely extending lower flange 32 connected thereto by means of a bight 30 . As seen in FIG. 1 , a conventional end cap 34 is utilized to seal the end of gutter 14 .
According to this embodiment of the present invention, there is provided a gutter guard which is generally designed by reference numeral 36 which has a central mean planer portion 38 extending the length of gutter 14 . Main central portion 38 has a first side 40 , approximate back wall 16 and a second side generally designated by reference numeral 42 approximate front wall 20 . Central planer portion 38 is provided with a plurality of apertures 43 which, as may seen, extend in diagonal rows in an angle of 45 degrees with respect to the length of gutter guard 36 .
At first side 40 , gutter guard 36 has an inner vertical wall 44 and an outer vertical 48 connected by a bight 46 . In turn, at the lower of outer vertical wall 48 , there is provided an inturned flange 50 .
At the second side 42 of gutter guard 36 , there is provided a vertical overflow wall 52 which is designed to prevent overflow during periods of heavy rain. Vertical overflow wall 52 terminates in a bight 54 which connects with an horizontal segment 56 . In turn, horizontal section 56 continues on through bight 60 and terminates in an inturned flange 58 .
Screws 62 are used to secure both the gutter 14 and gutter guard 36 to supporting structure 12 . Thus, it may seen in FIG. 3 , a screw 62 will extend through both inner vertical wall 44 and outer vertical 48 of gutter guard 36 and also thru back wall 16 of gutter 14 . The inturned flange 50 helps maintain proper tension on the device.
Similarly, screws 64 are used at the second side 42 to secure gutter guard 36 to gutter 14 . Again, the use of inturned flange 58 helps prevent loosening of the screws 64 .
Turning to the embodiment illustrated in FIGS. 4 and 5 , similar reference numerals with a prime are utilized for similar components. There is provided a gutter guard member generally designated by reference numeral 68 to be used in conjunction with a gutter (only a portion shown) having a back wall 16 ′ and the upper vertical segment 26 ′ of a gutter front wall. Gutter guard 68 includes a central planer portion 38 ′ having a first side 40 ′ and a second side 42 ′. Apertures 43 ′ extend through the central planer portion 38 ′.
At the first side 40 ′, gutter guard 68 has an inner vertical wall 44 ′. However, at the upper end of inner vertical wall 44 ′, there is provided a top wall segment 76 and then a downwardly angled segment 78 . By means of bight 80 , there is also provided an upwardly angled segment 82 . Downwardly angled segment 78 and upwardly angled segment 82 form a U-shaped configuration which are designed to receive one end of a sealing element 84 with the other end thereof being abutted against supporting structure 12 ′.
At the second side 42 ′, guard member 68 has a structure substantially identical to that of gutter guard 36 . Thus, there is provided a vertical overflow wall 52 ′, a bight 54 ′, and a horizontal segment 56 ′. At the distal end of horizontal segment 56 ′, there is provided an inturned flange 58 ′ which is connected thereto by means of a bight 60 ′.
As with the case of the previously described embodiment, a screw 62 ′ is utilized to secure back wall 16 ′ to supporting structure 12 ′. However, this embodiment also provides for a hook member 86 having a U-shaped portion 88 at one end thereof. Hook 86 is also attached by means of a screw 62 while hook 86 engages in the portion between upper inwardly extending flange 28 ′ and lower flange 32 ′. It will also be noted that screw 64 ′ is utilised to retain guard 68 in place as in the previously described embodiment.
As the guard 68 may be provided in a plurality of pieces for retrofitting, a connector 90 may be utilized which fits within the space defined by downwardly angled segment 72 , inner vertical wall 44 ′, and a central planar portion 38 ′.
A slightly modified arrangement of the embodiment of FIGS. 4 and 5 is shown in FIG. 6 . In this arrangement, it will be noted that hook 86 ″ is somewhat angled while after the first side 40 ″, there is provided a downwardly angled wall segment 92 between planar portion 38 ″ and inner vertical wall 44 ″.
Turning to FIG. 7 , there is illustrated another arrangement wherein there is provided a first upwardly extending portion 94 from planer central portion. Upwardly extending portion 94 reverses itself in a U-shaped configuration to provide an underlying portion 96 joined by means of bight 98 . A further bight 100 leads into a third section 102 . Between sections 96 and 102 , there is provided a U-shaped portion arranged to accept a sealing strip 104 .
It will be understood that the above described embodiments are for purposes of illustration only and changes and modifications may be made thereto without departing from the spirit and scope of the invention. | A device for protecting a gutter having a rear wall, front wall and a bottom wall, the walls defining a trough there between, the device comprising a guard member having generally planar central portion with one side thereof having an inverted U-shaped configuration designed to fit over an upper marginal edge of the rear wall of the gutter while at the other side, there is provided an overflow wall. The guard and gutter are attached directly to a supporting structure by means of screws or other mechanical fastening devices. | 4 |
CROSS REFERENCE TO RELATED APPLICATIONS
This is a continuation of application Ser. No. 08/567,735 filed on Dec. 5, 1995 now U.S. Pat. No. 5,653,748, which is a file-wrapper continuation of application Ser. No. 08/420,135, filed Apr. 11, 1995, now abandoned, which is a continuation of application Ser. No. 07/886,518, filed May 20, 1992, now U.S. Pat. No. 5,405,378.
BACKGROUND OF THE INVENTION
The invention relates to a device with a prosthesis implantable in the body of a patient, especially in a blood vessel or other body cavity, and designed as a hollow body, said prosthesis being compressible against the action of restoring spring forces down to a cross section which is reduced relative to an (expanded) operating position, said prosthesis also automatically expanding to a cross section corresponding to the operating position following removal of the restraining forces effecting the compression.
Devices of this type are known, and serve for percutaneous implantation of vascular prostheses in particular. Prostheses which are introducible percutaneously and expand in the lumen are either expandable mechanically by means of a known balloon catheter from a small radius to the larger radius to hold a vascular lumen open, or they expand automatically following previous compression prior to implantation by spring force, due to spring pretensioning generated during compression.
Various systems are already known for inserting self-expanding vascular prostheses which are under spring force into the body of a patient, and to implant or anchor them in the vessel by removing the restraining force.
The commonest method, which is described in EP-A-0 183 372, consists in compressing an endoprosthesis, made in the form of a tubular hollow body, to a reduced cross section and then pushing it in the compressed state, using a so-called pusher, through a catheter previously introduced into a vessel until they are in the correct position in the vessel. However, this system suffers from the disadvantage that a considerable expenditure of force is required to push the prosthesis through the catheter because its displacement is counteracted by considerable frictional forces.
Another method (not confirmable by publications) consists in retracting a sheath covering the endoprosthesis and holding the latter together, in the vessel at the implantation site. Here again there is the disadvantage that high frictional forces must be overcome. Moreover, the tube system is quite rigid because of the sheath covering the prosthesis, making introduction into a vessel through curves very difficult.
In another system (U.S. Pat. No. 4,732,152) a woven and spring-tensioned prosthesis is held together in the compressed state by a double sheath, sealed at the distal end. This sheath is retracted from the folded prosthesis like a stocking being pulled off the foot of a wearer. To reduce the friction which then occurs, liquid can be introduced between the two sheath layers. This system, which initially appears elegant because of the reduction of the frictional resistances, is extremely cumbersome to handle however and requires two persons to operate.
SUMMARY OF THE INVENTION
The invention is intended to provide an especially simple and readily operable device for implantation of a prosthesis made in the form of a hollow body, with a vascular prosthesis envisioned in particular.
This goal is achieved by virtue of the fact that in the device the prosthesis is surrounded by a sheath which can be pulled off it, said sheath consisting of at least one through thread, and compressed to a reduced cross section, and by the fact that at least one drawstring is provided, said drawstring being laid so it extends away from the sheath holding the prosthesis in its radially compressed state, the thread forming said sheath being retractable.
In the invention, the prosthesis is therefore held in its radially compressed state by means of this external sheath and reaches its intended expansion position only after removal of this sheath, which is designed to be pulled off, thanks to the pretensioning force generated during compression.
The sheath can be in particular a meshwork produced by crocheting, knotting, tying, or other methods of mesh formation.
Advantageously the prosthesis, held by the sheath which can be pulled off in the radially compressed state, can be received on a probe, or a flexible guide wire, and advanced thereon. In one design of a device of this kind, implantation is accomplished by introducing the guide wire in known fashion into a vessel and then advancing the prosthesis, held in a radially compressed state, along the guide wire, said wire being advanced for example by means of a sleeve likewise advanced over the guide wire and engaging the end of the prosthesis away from the insertion end thereof.
Another improvement, on the other hand, provides that the prosthesis, held in the radially compressed state by the sheath which can be pulled off, is held in an axially fixed position on the insertion end of a probe. Specifically, this probe can be a catheter advanced over a guide wire.
Even with the axially fixed mounting of the prosthesis, held in the compressed state, on the insertion end of a probe or a catheter, implantation takes place in simple fashion with the probe or catheter being advanced together with the prosthesis mounted on the insertion end, for example under the control of x-rays, up to the implantation site, and then by pulling off the sheath, made for example as a covering meshwork, the prosthesis is exposed and implanted in the proper location by its automatic expansion.
In mounting the prostheses on the insertion ends of probes or catheters, it has been found to be advantageous for the prosthesis to be mounted on a non-slip substrate surrounding the probe or catheter, so that undesired slipping and sliding during the release of the thread material forming the meshwork cannot occur.
Advantageously, the self-expanding prosthesis can be a tube made by crocheting, knitting, or other methods of mesh formation, composed of metal and plastic thread material with good tissue compatibility, said tube being compressible radially against the action of pretensioning forces and automatically expanding into its operating position after the restraining forces are removed, and then remaining in the expanded position.
In the case of the prosthesis designed as meshwork, according to a logical improvement, successive rows of mesh can be made alternately of resorbable thread material and non-resorbable thread material. This means that within a predetermined period of time after implantation, the resorbable thread material will be dissolved and the prosthesis parts, then consisting only of non-resorbable thread material, will remain in the patient's body. These remaining components form circumferential rings of successive open loops. This avoids thread intersections which could exert undesirable shearing forces on surrounding and growing tissue coatings.
In the improvement just described, drugs can also be embedded in the resorbable thread material so that the prosthesis constitutes a drug deposit which gradually dispenses drugs during the gradual dissolution of the resorbable thread material.
An especially advantageous improvement on the invention is characterized by making the tubular meshwork holding the prosthesis in the compressed state in such a way that the mesh changes direction after each wrap around the prosthesis and when successive meshes are pulled off, the thread sections forming the latter separate alternately to the right and left from the prosthesis.
The advantage of this improvement consists in the fact that the mesh wrapped successively and alternately left and right around the prosthesis can be pulled off without the thread material becoming wrapped around the probe holding the prosthesis or a catheter serving as such, or undergoing twisting, which would make further retraction of the thread material more difficult because of the resultant friction.
It has also been found to be advantageous in the improvement described above for the loops or knots of the mesh wrapped successively around the prosthesis and capable of being pulled off, to be located sequentially with respect to one another or in a row running essentially axially.
Another important improvement on the invention provides for the drawstring to extend away from the mesh surrounding the insertion end of the prosthesis, and therefore the prosthesis, as the meshwork is pulled off its distal end, gradually reaches its expanded position.
In this improvement, the thread material to be pulled off when the prosthesis is tightened can never enter the area between the already expanded part of the prosthesis and the wall of a vessel for example. The thread material to be pulled off instead extends only along the part of the mesh which has not yet been pulled off and thus in the area of the prosthesis which is still held in the compressed position.
The ends of the thread material forming the meshwork can be held by releasable knots, in the form of so-called slip knots for example, and thereby have their releasability preserved. One especially simple means that has been found for axial mounting of the prosthesis on a probe or on a catheter serving as such is for the beginning of the thread material forming the meshwork and an end mesh to be pinched in holes in the probe or catheter, yet capable of being pulled out of their pinched positions by means of the drawstring. The beginning of the thread material can be pinched between the probe and the cuff mounted held on the latter, however.
The cuff material is held especially securely, but at the same time in such a way that it can be easily pulled off, if from the knot of the mesh of the first mesh on the pull-off side of the meshwork, a loop passed through a hole extends, one end of said loop making a transition in the vicinity of the above knot to the drawstring. As a result, this loop can be pulled off by means of the drawstring through the above-mentioned knot and then all of the mesh forming the meshwork can be pulled off in succession.
According to another logical improvement on the invention, the prosthesis can also be held in its radially compressed position by means of a meshwork applied from the distal end of the probe or catheter and extending over the insertion end of the prosthesis and by means of a meshwork that extends in the direction opposite the proximal end and also extends over the end mesh of the first meshwork. It has been found advantageous in this connection for the two meshworks to be capable of being pulled off in opposite directions from their loop-shaped end meshes by means of drawstrings.
In a design of this kind, following correct placement of the prosthesis mounted on a probe or a catheter in a vessel, the meshwork applied from the distal end is pulled off first, beginning with the end mesh removed from the distal end and then advancing gradually until this meshwork is removed completely and the thread material is retracted. Then the meshwork applied from the proximal end is pulled off, starting with the end mesh toward the distal end and then advancing toward the proximal end. It is obvious that when the meshwork is pulled off in this way, the self-expanding prosthesis is expanded gradually, starting at its distal end, into its intended operating position.
In another important embodiment, the sheath that holds the prosthesis in its radially compressed position consists of loops surrounding the prosthesis and spaced axially apart, said loops being formed by the thread material, pulled through a hole in the prosthesis, of a thread guided along inside the prosthesis,.with the ends of the loops each being brought back through a hole, adjacent to the first hole in the circumferential direction, into the interior of the prosthesis, and a warp thread, likewise running along the inside of the prosthesis and guided through the ends of the loops, holds in the loops in their wrapping positions. It is clear that in this design the prosthesis is released by pulling the warp thread out of the end segments of the loops, and that the thread material forming the loops,like the warp thread, can be retracted in simple fashion. In a similar improvement on the invention, the sheath holding the prosthesis in its radially compressed position consists of loops which are axially spaced apart and are wrapped around the prosthesis, said loops being formed by thread material, pulled through a hole in the prosthesis, of a thread guided along inside the prosthesis, with the ends of the loops each being brought back into the interior of the prosthesis through holes spaced axially from the first hole, and held in place by the fact that a loop formed from the thread material running inside the prosthesis is pulled through each loop end brought back into the prosthesis, said loop then being brought out through a hole following in the axial direction, then being wrapped around the prosthesis and brought back in the same manner with its loop end passing through a hole into the prosthesis and being secured in this position. In this design also, the pulling off of the sheath holding the prosthesis in its radially compressed position is accomplished in simple fashion by means of the thread extending from the last loop, from which the loops surrounding the prosthesis are formed.
For especially tight wrapping and the resultant compression of the prosthesis, it has also been found advantageous to use shrinkable thread material to form the meshwork. The meshwork that can be pulled off can also consist of a plurality of threads running parallel to one another.
Another important improvement on the invention provides that between the prosthesis and the sheath holding the latter in the radially compressed state, at least one additional sheath is provided which loosely fits around the prosthesis and allows a partial expansion of the prosthesis when the outer sheath is pulled off, and is itself subsequently capable of being pulled off.
This improvement is also one that involves a sheath, surrounding the prosthesis loosely and with a certain amount of play, being mounted on said prosthesis, which can be a meshwork, with the prosthesis and the inner sheath being surrounded closely by an outer sheath which holds the prosthesis, together with the sheath mounted directly on it, in the radially compressed state. The prosthesis is consequently surrounded by two layers, so to speak, and after the outer sheath is stripped, can expand only within the limits set by the inner sheath. The final implantation is then accomplished by stripping the inner sheath, i.e. in stages.
Of course, several meshworks surrounding one another with a certain amount of play can be provided, which permit expansion of the prosthesis in several successive stages.
Within the scope of the invention, the spaces between the meshes of a meshwork surrounding the prosthesis and holding it in the compressed state can be filled and smoothed with gelatin or a similar substance which dissolves in the body of a patient. This facilitates introduction of such a device.
According to yet another improvement, at least one end of the prosthesis can be surrounded in the compressed state by a cuff, said end, because of the axial shortening of the prosthesis that takes place during expansion, escaping the grip exerted by the cuff. A cuff of this kind can be mounted permanently on the probe and/or a catheter, with the open side facing the prosthesis, for example on the side toward the distal end. This produces a smooth transition that facilitates introduction, at the end of the prosthesis which is at the front in the insertion device.
For improved attachment of the prosthesis to a probe or a to catheter serving as same, the end of the prosthesis facing away from the insertion end can abut the end of the prosthesis away from the insertion end at a radially projecting step or shoulder or a cuff mounted on the probe or catheter.
Yet another improvement on the invention provides that when a catheter is used as a probe, the drawstring is introduced through a hole passing through the catheter wall in the vicinity of one end of the prosthesis, enters the lumen of the catheter, extends through the latter, and extends beyond the end of the catheter.
However, a double-lumen catheter can also serve as a probe with one lumen serving to advance the catheter over a guide wire and the other lumen being used to guide the drawstring.
When using a catheter with one or two lumina as a probe, with the drawstring passing through the catheter lumen, assurance is provided that the walls of the vessels or other body cavities in which a prosthesis is to be implanted cannot be damaged by the drawstring and/or, when the meshwork is stripped, by the thread material, which is then pulled back through the catheter lumen.
It has also proven to be advantageous for the drawstring and/or the thread material of the meshwork to be provided with a friction-reducing lubricant.
In addition, at least the drawstring can be made in the form of a metal thread or provided with an admixture of metal, so that good visibility with x-rays is ensured.
Finally, according to yet another improvement, the prosthesis, kept in the radially compressed position by the strippable sheath, can expand to resemble a trumpet at its proximal end in the expanded state following removal of the sheath. This prosthesis design is important for implants in the vicinity of branches in the vessels, because there is always the danger of the prosthesis slipping into the branching vessel. In view of the trumpet-shaped expansion at the proximal end, however, such slipping during implantation is effectively suppressed when the sheath surrounding the prosthesis is stripped off the proximal end.
One embodiment of the device according to the invention will now be described with reference to the attached drawing.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a catheter with a vascular prosthesis mounted on its distal end held under radial pretensioning in the compressed state by a crocheted material in the form of a strippable tubular meshwork;
FIG. 2 is a view showing the formation of an initial mesh of crocheted material on the prosthesis, with a loop brought around the vascular prosthesis on the right side;
FIG. 3 is a view like that in FIG. 2, showing the formation of a crocheted mesh adjoining the initial mesh, wrapped around the vascular prosthesis on the left side;
FIG. 4 is a view similar to FIG. 1 showing a design for a device in which the vascular prosthesis mounted on the catheter is held in its compressed state with radial pretensioning by means of strippable crocheted material mounted on the distal and proximate ends;
FIG. 5 shows the device according to FIG. 4 but with the crocheted material applied from the distal end;
FIG. 6 shows the device according to FIG. 4 with the crocheted material applied from the proximal end alone, eliminating the crocheted material shown in FIG. 5;
FIG. 7 shows the vascular prosthesis alone, held in a radially compressed position by wrapping loops;
FIG. 8 is a view like that in FIG. 7 of a prosthesis in which the loops holding the latter in a radially compressed position are formed by crocheting, and
FIG. 9 shows partial stripping of a vascular prosthesis in the form of knitted fabric.
DETAILED DESCRIPTION OF THE INVENTION
In device 10 shown in FIG. 1, an elongated catheter 11 serves as a probe, with a through lumen by which the catheter can be advanced in known fashion over a guide wire inserted in a vessel. In the vicinity of its distal end 12, catheter 11 carries a prosthesis 15 held in a compressed position under radial pretensioning by means of a crocheted material 14, said prosthesis, following elimination of the restraining force provided by the crocheted material, changing to its intended expanded position by expanding automatically. For example, the prosthesis can be a tubular knitted fabric radially compressible against the effect of a restoring spring force into a position in which it fits closely around the catheter in the vicinity of its distal end.
Prosthesis 15 is surrounded by a crocheted material 14 formed by a continuous thread, with successive meshes wrapped around the prosthesis alternately on one side or the other, in other words alternately on the right or left side. The initial section 17 of the thread material, located in front of the first mesh 16 associated with the distal end 12 of catheter 11, is pulled through a slot 18 in the catheter wall, pinched in said slot, and then extends through the catheter lumen and out through the distal end of the catheter. A strippable loop 22 is pulled through a knot 21 that closes end mesh 21 which is remote from the distal end, said loop being pulled through two rejected [sic. "beanstandete"] cuts 23, 23' in the catheter wall, and is therefore likewise held axially by pinching.
The free thread end guided through knots 21 of said end mesh 20 forms a drawstring 24 extending along catheter 11, by means of which drawstring, first loop 22 held on the catheter by pinching and then gradually the mesh formed of crocheted material extending around the prosthesis and holding the latter in its compressed state, can be stripped through said end knot. Since the meshes are wrapped alternately right and left around prosthesis 15, when the mesh is stripped the threads on the right and left sides of the catheter are released alternately from the corresponding mesh knots, and after the mesh facing the distal end comes loose, initial segment 17 of the thread material can be pulled out of its pinched position in slot 18 at distal end 12 of catheter 11.
In an enlarged view, FIGS. 2 and 3 show the mesh formation with alternate front and back wrapping of catheter 15, which in these figures is shown as a rigid tubular structure for the sake of simplicity. After securing initial section 17 of the thread material in the manner shown in FIG. 1 by pinching in slot 18, the thread is wrapped around the catheter, then a loop 26 is pulled through under the thread, and then from free thread material 27, a mesh on the back of the catheter is pulled around the latter and passed through loop 26, whose section pulled through the above loop 26 in turn forms a loop 28 to form the next mesh. FIG. 2 shows free thread material 27 in solid lines before it is pulled through loop 26, and shows it in dashed lines after it is pulled through this loop and forms loop 28 for the next mesh.
To form the next mesh, as shown in FIG. 3, forming another loop 30 in the manner shown by the dashed lines, the free thread material is pulled out of the position shown at 31 in front of the catheter, through previously formed loop 28, and then this process of loop and mesh formation is continued, with the thread material pulled alternately behind and in front of the catheter through the respective loops until the prosthesis held in the catheter is crocheted over its entire length.
Loop 22, pulled through the loop associated therewith or through a knot 21 formed by pulling together these loops to form end mesh 20, is then pulled in the manner shown schematically in FIG. 1 through the two axially spaced slots 23, 23' in the wall of the catheter and held in place by pinching. The remaining thread material then forms drawstring 24 which extends from the loop of end mesh 20 and permits the crocheted material to be stripped, with the thread material of the meshes as they are stripped alternately coming loose on one side or the other of prosthesis 15, thereby releasing the prosthesis to expand under the pretensioning force imposed during crocheting as a result of radial compression.
In embodiment 40 shown in FIG. 4, a prosthesis 45 is mounted and held in its compressed position under radial pretensioning on an elongated catheter 41 in the vicinity of distal catheter end 42. This purpose is served by crocheted material 46, 47 shown in FIGS. 5 and 6. Catheter 41, like catheter 11 of the embodiment shown in FIG. 1, is advanceable by means of a guide wire located in a vessel, in said vessel so that prosthesis 45 mounted on the catheter is implantable positionwise in the vessel prior to its implantation by stripping the crocheted material.
The crocheted material that holds prosthesis 45 in the compressed position shown in FIG. 4 is applied sequentially, with crocheted material 46 starting at the distal end. The other crocheted material 47 is applied from the proximal end and then overlaps the end of the first crocheted material 46.
FIG. 5 shows that catheter 41 is provided on the distal end with a silicone cuff 43, which serves to hold the initial segment 48 of the thread required for the formation of the first crocheted material. For this reason, initial segment 48 of this thread is pulled through beneath silicone cuff 43. Then the first meshes 49, in the manner explained above in conjunction with FIGS. 1 to 3, are crocheted on catheter 41, and provide a firm seat on the catheter for the first crocheted material. subsequent meshes 50 fit over the end of prosthesis 41 that points toward the distal end of the catheter, and compress the latter under radial pretensioning with simultaneous axial immobilization of the prosthesis on the catheter, as shown in FIG. 5. A final mesh 51 of this crocheted material 46 is then applied externally on prosthesis 45, with thread 52 extending from this mesh as a drawstring to strip the mesh of the above-mentioned crocheted material.
FIG. 6 shows the application of the second crocheted material 47 from the proximal end. Beginning 55 of the thread material of this crocheted material is again held by means of a silicone cuff 54 pulled onto the proximal end of catheter 41, while the beginning of the thread is pulled through beneath this cuff. Then several meshes 56 are crocheted onto the catheter in the direction of the distal end, followed by additional meshes 57, while wrapping prosthesis 41 during its simultaneous radial compression up to and beyond meshes 50, 51 of the first crocheted material 46 facing away from the distal end, which are held thereby. A last mesh 58 of the crocheted material 47 applied from the proximal end is then pulled through under silicone cuff 43 pushed onto the distal end of the catheter, and held thereby. In addition, thread 60 extends from the end mesh facing the distal end of the crocheted material 47 applied from the proximal end, as a drawstring to strip the mesh of this crocheted material.
The prosthesis 45 in the embodiment shown in FIGS. 4 to 6, like that in the embodiment shown in FIGS. 1 to 3, is held under radial pretensioning in the compressed position on catheter 41 and automatically expands to its expanded position after removal of crocheted material 46, 47. Following introduction of the prosthesis mounted on the catheter into a vessel and its location in place, implantation occurs in such fashion that crocheted material 46 applied from the distal end is removed first. This is accomplished by stripping the mesh of this crocheted material by means of drawstring 52, with mesh 51 located beneath the crocheted material applied from the proximal side being stripped first and then gradually meshes 50 and 49 abutting the distal end being stripped until eventually the first mesh adjacent to silicone cuff 43 comes free and the beginning of thread 48 beneath the silicone cuff is pulled out.
Since the end of the prosthesis that points toward the distal catheter end is released by stripping crocheted material 46 applied from the distal end, this end of the prosthesis expands radially as a result of the pretensioning forces of the prosthesis itself, while the remaining part of the prosthesis is still held in the compressed position by crocheted material 47 applied from the proximal end. Partially expanded prosthesis 45 is axially immobilized in this position both by the adhesive effect between the catheter and the prosthesis and by a silicone cuff 62 mounted on the proximal end of prosthesis 45 on catheter 41, which cuff the prosthesis abuts axially.
After stripping first crocheted material 46, crocheted material 47 applied from the proximal end is also stripped, specifically by means of drawstring 60 extending from its end mesh 58 on the side pointing toward the distal end. It is clear that when the drawstring is pulled, loop 58 held at the distal end beneath silicone cuff 43 is stripped first and then meshes 57 and 56 are stripped, starting at the side facing the distal end, gradually in the direction of the proximal end, with prosthesis 45 expanding radially and abutting the walls of a vessel to be equipped with a prosthesis. At the end of the stripping process, thread end 55 located beneath silicone cuff 54 at the proximal end is pulled free. Prosthesis 45 is then free of catheter 41 and the latter can be withdrawn in simple fashion out of the vessel.
Prosthesis 70 shown in FIG. 7 is likewise tubular in shape and self-expanding. It can be a meshwork, roughly in the form of a knitted fabric. The prosthesis is provided with holes 71, 72 associated with one another pairwise and located at approximately equal axial distances from one another. Loops 74 surrounding the prosthesis externally hold the prosthesis together in its radially compressed state. These loops are thread material, each pulled through a hole 71, of a thread 75 running along the inside of the prosthesis, said thread then surrounding the prosthesis forming a loop with tension, and with loop end 76, each being introduced through a hole 72 corresponding to matching hole 71, back into the interior of the prosthesis. The loops are held in the wrapping position shown in FIG. 7 by means of a warp thread 78 guided through loop ends 76 inside the prosthesis.
The advantage of the embodiment shown in FIG. 7 consists in the fact that loops 74 wrapped around the prosthesis at essentially constant axial intervals are used as means for radial compression. of prosthesis 70, said loops having no external knots at all but formed by a thread 75 running along the inside of the prosthesis and held in the tensioned position by means of the warp thread 78 likewise running along the inside of the prosthesis.
The prosthesis according to FIG. 7, in the same way as described above in conjunction with FIGS. 1 to 6, is mounted in a radially compressed state on a catheter in the vicinity of the distal catheter end, and is implantable by means of the catheter by advancing the latter in a vessel. Following correct positioning in the vessel, implantation is accomplished in simple fashion by pulling warp thread 78 out of ends 76 of loops 74, whereupon prosthesis 70 expands radially under its own spring pretensioning force to its proper expanded position. Thread 75 which is pulled to form the loop can then likewise be simply pulled back.
The embodiment shown in FIG. 8 differs from the embodiment in FIG. 7 in that loops 74 surrounding prosthesis 70' and spaced axially apart are formed by crocheting. Through a hole 71' in the prosthesis, thread material from thread 75 guided along the interior of the prosthesis is pulled out and wrapped as a loop 74' around the prosthesis, and is also introduced through a hole 72' spaced axially from above-mentioned hole 71', together with loop end 76', back into the interior of the prosthesis. Thread material is then pulled through this loop end 76' located in the interior of the prosthesis, forming another loop and guided externally through a hole 71' following in the axial direction, then is wrapped again around the prosthesis as loop 74' and secures the loop end, brought back into the interior of the prosthesis through another hole 72', in the same manner as the first loop.
Referring to FIG. 9, a knitted intravascular prosthesis 80 (partial view to illustrate component threads) is shown in which a thread 81 of resorbable material and a thread 82 of non-resorbable material are knitted together alternately. The non-resorbable thread material can be tantalum for example.
The advantage of this prosthesis design consists in the fact that the resorbable thread material dissolves following expiration of a predetermined period of time after implantation, and then only the non-degradable components remain in the body of a patient. These remaining components form circular rings of successive open loops. In this manner, thread crossings are avoided, which could exert unnecessary shearing forces on the surrounding and growing tissue coatings.
Prostheses can also be designed in simple fashion as drug deposits with drugs being imbedded in the resorbable thread material and released as this material degrades. | The device comprises a prosthesis designed as a hollow body compressed against the action of restoring spring forces to a cross section reduced relative to an expanded use position, and held in this position by a strippable sheath. After the sheath is stripped, the prosthesis automatically expands to a cross section corresponding to the use position. The sheath, which can be a meshwork in the approximate form of crocheted material, extends over the entire length of the prosthesis and consists of at least one continuous thread and at least one drawstring. The prosthesis, held in the radially compressed position by the sheath, can be mounted displaceably on a feed wire or non-axially-displaceably on the insertion end of a probe or a catheter. | 3 |
FIELD OF THE INVENTION
The present invention relates to an apparatus configured to support garment, particularly trousers and towels.
BACKGROUND OF INVENTION
Most garment hangers comprises of a hook, two supporting arms, extending in opposite directions from a medial portion, and a horizontal supporting bar connecting the two remote ends of the supporting arms to form a triangular frame. While the two supporting arms are configured to support the shoulder portion of a shirt or jacket, the supporting bar is used for hanging a pair of trousers or towel. The disadvantage of a single supporting bar is that the trousers wrap over the supporting bar tends to slip and fall during movement. In order to hang the trousers, the user is required to dress the trousers through the center hole of the triangular frame and then properly align the trousers on the supporting bar. This operation is quite inconvenient. It is the objective of the subject invention to provide a cost effective improved design of trousers supporting bars to facilitate putting the trousers onto the hanger and to provide reliable non-slipping function.
The prior art is replete with various configurations of garment hangers with dual supporting bars structured for hanging trousers and to provide non-slipping function. U.S. Pat. Nos. 2.226,786; 2,244,355; 2,340,320; 2,347,949; 2,420,196; 3,201,016; 3,402,866; 4,895,283; 5,040,707 and 5,137,191 exemplify such constructions.
SUMMARY OF THE INVENTION
The present invention is directed to a garment hanger configured with two supporting bars for supporting trousers or towels. The design objective of this invention is to provide a cost-effective solution for an easy to use and non-slipping trousers supporting hanger.
In a preferred embodiment of the invention, the trousers supporting hanger comprises two supporting bars. The first supporting bar is a horizontal stationary bar, which is part of the hanger frame. Usually the hanger frame is also connected with a hook or an alternate suspension member. The second supporting bar is a movable bar configured to comfortably supporting a pair of trousers or a towel. On one end of the stationary supporting bar is a first vertical supporting portion connected to the upper part of the hanger frame. This portion is connected to a terminal end of the movable supporting bar by a design which allows the movable bar to swing, or rotate freely about the vertical supporting portion as the axis of rotation. When an user holds the hanger frame with one hand and slightly tilted the hanger forward, the movable supporting bar will swing by the gravitational force. The other terminal end of the movable supporting bar then becomes an open end ready to receive a pair of trousers. The freely rotational trousers supporting bar is difficult to manage with one hand operation. In order to facilitate the operation, it is a secondary objective of the invention to provide a structural design to limit the angle of the swing, stopping the movable bar at a convenient rotational angle for the user to dress the trousers onto the movable supporting bar. With this stopper, the user is not required to hold the movable supporting bar, while be able to manage the position of the movable supporting bar with the hand that holds the hanger frame. This design set free the other hand of the user to fetch the trousers and align it properly onto the movable supporting bar.
Once the trousers are properly positioned onto the movable supporting bar, the user may lift up the open end of the movable supporting bar and bring it to a locking position located proximate to the other terminal end of the fixed supporting bar. There are various kinds of locking and release design suitable to serve this purpose. It is another objective of this invention to introduce a simple, low cost and easy to operate lock and release mechanism for the two supporting bars to engage or disengage. It is yet another objective of the invention to provide a low cost design enabling the two supporting bars to hold the trousers and prevent it from slipping during movement. In a preferred embodiment, the stationary supporting bar comprises a second supporting portion connected to the hanger frame. This second supporting portion is structured to provide an upper portion and a lower portion in the shape of a step. The upper supporting portion provides a span wider than the length of the movable supporting bar and therefore allowing the movable supporting bar to move around, or swing to a wide open position to receive a pair of trousers. The lower supporting portion provides a span shorter than the effective length of the movable trousers supporting bar, thus restraining the movement of the movable supporting bar. At the end of the open end terminal of the movable supporting bar is provided with a latch, a slot or any mechanical design enabling the movable supporting bar to engage the lower supporting portion of the stationary supporting bar.
Another characteristics of the preferred embodiment is that once placed in a locking position, the two ends of the movable supporting bar are restrained from moving except into the upward direction. With this design, the trousers supporting bars is self adjusted to support trousers or towel of different thickness. The free vertical movement of the trousers supporting bar also helps to create a pressure to clamp the trousers with the two supporting bars, with the movable supporting bar on top of the trousers, and stationary one at the bottom. The pressure formed is defined by the weight of the movable supporting bar and also the gravitational weight of the trousers. The higher the force pulling the trousers in the downward direction, the higher is the pressure inserted onto the movable supporting bar to hold the trousers in position. The locking and release design allowing free vertical movement is thus a preferred characteristic to support the non-slip function. It is therefore anticipated that the preferred embodiments of the invention comprise the following characteristics, such as the freely rotational supporting bar, free vertical movement of the rotational mechanism, the easy to operate lock and release mechanism combining with the free vertical movement at the locking mechanism, and the stopper helping to control the position of the movable supporting bar in the unlock position, just with the hand holding the hanger frame. All these elements contribute to a cost effective and better-performed trousers supporting hanger.
Although detailed embodiments of the invention have been disclosed, it is recognized that variations and modifications, all within the spirit of the invention, will occur to those skilled in the art. It is accordingly intended that all such variations and modifications be encompassed by the appended claims.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a front view of a garment supporting apparatus showing a preferred embodiment in accordance with the present invention.
FIG. 2 is a side view illustrating a trousers bar mounted on top of the metal wire supporting bar;
FIG. 3 is a top view of the trousers bar;
FIG. 4 is a side view showing the remote end of the metal wire supporting bar being configured to form a step for accepting the trousers bar in a locking position.
FIG. 5 illustrates the operation of a preferred embodiment of the locking mechanism.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 is an elevation view illustrating a preferred hanger embodiment 100 in accordance with the present invention. The garment supporting apparatus 100 includes a suspension member 103 ; a medial portion 202 ; two supporting arms 101 and 102 configured to support the shoulder portion of a garment; a horizontal supporting bar 111 made with a metal wire; and a trousers supporting bar 121 configured to swing or rotate about a terminal end of the metal wire bar 111 .
On one end of the metal wire supporting bar is a supporting portion 112 connecting the metal wire to one end of the supporting arm 102 . The other end of the metal wire supporting bar 111 is formed to provide a step represented by the portions 113 and 114 . The tip of the portion 113 is connected to the end of another supporting arm 101 . The upper portion 113 of the step provides a wider span measured from the remote supporting portion 112 than the lower portion 114 .
The trousers supporting bar 121 has a terminal end 122 engaged with the end of the metal wire supporting bar 111 . The terminal end 122 of the trousers supporting bar has a hole designed to accommodate the metal wire of the supporting portion 112 ; so as to enable the trousers supporting bar 121 to freely swing or rotate without any constrain from the metal wire supporting bar 111 . The metal wire supporting portion 112 defines the axis of rotation.
One or more stoppers 123 and 124 are provided to limit the angle of rotation in between the trousers supporting bar 121 and the metal wire supporting bar 111 . The stoppers are very important parts of the invention as they enable the trousers supporting bar to swing and stay at a reasonably wide open position as illustrated in FIG. 1, allowing an user to dress a pair of trousers or a towel through it's free end 125 . Under normal operation, the user holds the supporting arm 102 with the right hand, then tilted the garment hanger 100 slightly forward. Then the trousers supporting bar will swing away from the metal wire supporting bar 111 due to the gravitational force of the trousers supporting bar 121 . The trousers supporting bar 121 is preferably be allowed to rotate along the axis 112 freely for the gravitational force principle to work. After the trousers or towel is properly placed on the supporting bar 121 , the user lifts up the open end terminal 125 with the left hand, bring it to the upper supporting portion 113 of the step and then let the slot 126 of the trousers supporting bar 121 engage with the lower supporting portion 114 of the step, to form a locking position. The two side walls of the slot is engaged with the lower portion 114 and prevent the trousers supporting bar 121 from removal until the terminal end 125 is lifted upward above the lower supporting portion 114 .
It should be noted that the pivoting end 122 is always resting on top of the metal wire supporting bar 111 . When the trousers supporting bar is positioned in the locking position, the trousers supporting bar 121 also rests on top of the metal wire supporting bar 111 and both terminal ends 125 and 122 are free to move upward from the metal wire supporting arm 111 . In this position, the pressure in between the trousers supporting bar 121 and the metal wire supporting bar is defined by the gravitational weight of the trousers supporting bar 121 . When a pair of trousers or a piece of towel is wrapped around the trousers supporting bar in the locking position, the pressure in between the two bars is also defined by the gravitational weight of the trousers or towel. This phenomenon is important as the heavier the weight of the trousers or the higher the downward pulling force of the trousers, the higher is the pressure formed in between the two bars which are positioned one on top of the other. This working principle provides an excellent non-slipping solution to the trousers supporting bar.
FIG. 2 illustrates a side view showing the relative positions of the two supporting bars in the locking position. The trousers supporting bar 121 is positioned on top and parallel to the metal wire supporting bar 111 . It can be observed that the terminal end 122 of the horizontal trousers supporting bar 121 is free to move in the upward direction, along the axis of the vertical supporting portion 112 . If the terminal end 122 is designed to be tight fit with the vertical supporting portion 112 of the metal wire, the other remote terminal end of the trousers supporting bar can only be lifted with the elasticity of the trousers supporting bar, which is possible only when the supporting bar is made of elastic material. FIG. 2 also demonstrates how the stopper 123 interacts with the metal wire supporting bar 111 . It is observed that the stopper 123 comprises of a downward flange, which will touch the metal wire supporting bar when the stopping angle is reached, and therefore prohibit the movement of the trousers supporting bar.
FIG. 3 illustrates the top view of the trousers supporting bar. The through hole 131 provides the pivoting or rotation axis when it is assembled with the vertical supporting portion 112 . The stoppers 123 and 124 extend from the front and rear sides of the trousers supporting bar 121 . The angle of the extension defines the stopping angle of rotation permitted by the trousers supporting bar relative to the metal wire supporting bar. At the other terminal end 125 of the trousers supporting bar is a slot 126 , which is configured to fit into the lower supporting portion 114 of the step formed by the two supporting portions 114 , 115 as illustrated in FIG. 1 . Because of the special shape and structural of the trousers supporting bar, it is most preferable to manufacture the trousers supporting bar with the injection molding process.
Attention is now drawn to FIG. 4 which illustrates a magnified top view of the terminal end 122 . The metal wire forming the vertical supporting portion 112 is dressed through the hole 131 located at the end of the trousers supporting bar 121 . The hole 131 is made larger than the diameter of the metal wire 112 so that the trousers supporting bar is free to swing, or rotate from the metal wire supporting wire 111 . The supporting portion 112 defines the axis of rotation.
When the hanger is slightly tilted forward, the gravitational force of the trousers supporting bar 121 will initiate the swing or rotational motion until the stopper 124 touches the metal wire supporting bar 111 . The location of the stopper 124 is carefully selected to provide a comfortable angle of opening as illustrated in FIG. 1 to facilitate the user to put in the trousers from the open terminal end 125 . Another stopper 123 may be added to provide the trousers supporting bar a limited swing angle towards the rear side of the hanger. It should be noted that although the stoppers 123 and 124 are symmetrical in the drawing, they may be modified to define different limiting angles.
FIG. 5 illustrates how the other remote terminal end of the trousers supporting bar is operated to provide the locking and release function. The supporting portions 114 and 113 extended from the metal wire supporting bar 111 is configured to form a step shape. The upper portion of the step 113 provides a width span wider than the length of the trousers supporting bar 121 and therefore allowing the trousers supporting bar to move around. The position of the trousers supporting bar 121 a demonstrates a unlocking or released position. When the terminal end 125 a of the released trousers supporting bar 121 a is dropped onto the lower supporting portion 114 of the step, the slot 126 of the trousers supporting bar as illustrated in FIG. 3 engaged with the lower supporting portion 114 to define a locking position. The two side walls next to the slot 126 prohibits the trousers supporting bar to move around except in the upward direction. It is observed that trousers supporting bars 121 a and 121 b define the released and locking position of the trousers supporting bar respectively.
Although a metal wire is used to form the horizontal supporting bar, it is anticipated that this metal wire bar can be made with different kinds of material or process as long as the free rotating function at the terminal end 122 and the engagement and locking function at the terminal end 125 are maintained. The trousers supporting bar 121 is preferable to be formed by die casting, metal forming or injection molding to provide the special shape of the stoppers 123 , 124 and the engagement mechanism 126 . Although the stoppers of the illustrated embodiment extends from the two sides of the trousers supporting bar, the design can be interchanged to provide a stopper bonded to the metal wire supporting bar to limit the rotational travel of the trousers supporting bar. It should also be noted that the rotational mechanism at the terminal end 122 and the engagement and locking mechanism 126 are exemplary. Different configuration able to provide the free rotation function and the releasable engagement/locking function are also included in the scope of this invention. Accordingly, it should be understood that the embodiments described herein are exemplary and that numerous modifications, dimensional variations, and rearrangements will occur to those skilled in the art to achieve equivalent results, all of which are intended to be embraced within the scope of the appended claims. | An garment supporting apparatus ( 100 ) is disclosed having a stationary horizontal supporting bar ( 111 ); a movable supporting bar ( 121 ); a mounting mechanism ( 112, 122 ) enables the movable bar to rotate freely relative to the stationary supporting bar at one of the terminal ends and a engaging mechanism ( 126, 114 ) having a step shape ( 113, 114 ) enabling the other terminal end of the movable supporting bar to engage or release from the other terminal end of the stationary supporting bar. | 0 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a workflow management system suitable for cooperative work spread over different organizations.
[0003] 2. Description of the Related Art
[0004] FIG. 1A and FIG. 1B are block diagrams illustrating a workflow model in the related art.
[0005] Specifically, FIG. 1A illustrates a workflow model of a fixed type. The entire flow, which includes five tasks T 1 through T 5 , is completely defined as a workflow before being performed, and the order relationship (illustrated by arrow solid lines in FIG. 1A ) of the tasks T 1 through T 5 is also defined when defining the workflow. Further, the number and configuration of the tasks do not change when the workflow is performed.
[0006] As for assignment of persons who perform the workflow, it is made as described below. A definition of the workflow is designed beforehand, persons who perform the workflow have roles defined in the workflow, and operations to be carried out are defined. When the workflow is performed, persons are assigned corresponding to the defined roles. Then, mail is sent to the assigned persons to notify them of the assignments, and newly assigned persons can choose to either accept or decline the assignments.
[0007] FIG. 1B illustrates a so-called AKW (Agile Knowledge Workflow) model, in which sub-tasks are added or deleted; thus the workflow is partially broken up (recursive division of sub tasks) while being performed, and flow control is performed based on a parent-child relationship and an order relationship of the tasks, and dependence of the input and output documents (Please refer to http://www.dfki.de/frodo/taskman/). For example, among tasks T 2 trough T 4 , which are children of task T 1 , task T 3 is further divided into tasks T 5 and T 6 while being performed. The order of performing the tasks is determined from the parent-child relationship and the explicit order relationship (precedence task relationship) of the tasks. In FIG. 1B , the order relationship is indicated by arrowed dashed lines.
[0008] As for assignment of persons who perform the workflow, tasks are added while the workflow is being performed, and persons who perform the workflow are assigned accordingly. Only summary and goal of the tasks are shown to be assigned to persons, and these persons carry out their work while the workflow is further divided. Similarly, a mail message is sent to the assigned persons to notify them of the assignments, and newly assigned persons can choose to either accept or decline the assignments.
[0009] The fixed-type workflow model, as shown in FIG. 1A , is suitable for typical work which can be classified in advance, whereas the AKW model as shown in FIG. 1B is suitable for work requiring high flexibility, which cannot be specifically analyzed and modeled in advance.
[0010] However, for cooperative work, or work without a specific solution procedure shared by different organizations, the above-mentioned fixed-type workflow model and the AKW model suffer from the following problems.
[0011] First, for the cooperative work shared by different organizations, it is difficult to reach an agreement in advance about detailed definitions of the workflow, the required skills cannot be anticipated, and further the roles in the workflow cannot be defined beforehand. Hence, the fixed-type workflow model cannot be adopted. Of course, the AKW model is usable in this sense.
[0012] Second, sometimes, it is desired that detailed operating procedures not be disclosed to partners involved in the cooperative work, but neither the fixed-type workflow model nor the AKW model can meet this need; in other words, neither the fixed-type workflow model nor the AKW model can hide information when necessary. For example, the following information needs to be hidden when necessary.
[0013] Specific personnel performing the cooperative work, which information is related to inside personnel;
[0014] Configurations of the children tasks, which information is related to specialized knowledge and technical know-how information;
[0015] Schedule progress of the children tasks, which information reflects whether the tasks are finished in a hurry near the deadline or completed with leeway, and also reflects the amount of actual operations; and
[0016] Intermediate outcomes, references, and other internal information required in the children tasks.
SUMMARY OF THE INVENTION
[0017] An embodiment of the present invention may solve one or more problems of the related art.
[0018] A preferred embodiment of the present invention may provide a workflow management system suitable for managing a workflow including plural hierarchically-classified tasks and for cooperative work spread over different organizations.
[0019] According to a first aspect of the present invention, there is provided a workflow management system for managing a workflow including a plurality of hierarchically-classified tasks, comprising:
[0020] a task receiving device configured to receive designation of a task to be delegated;
[0021] a delegatee receiving device configured to receive designation of a delegatee;
[0022] an acceptance receiving device configured to receive acceptance of a delegation from the delegatee;
[0023] a first processor that allows a delegator to hide a delegated task and a subordinate task, and allows the delegator to confirm status of the designated task; and
[0024] a second processor that allows the delegator to refer to other tasks relevant to the delegated tasks.
[0025] As an embodiment, the first processor changes owners of the delegated task and the subordinate task to be the delegatee, duplicates bibliographical information from the delegated task, and creates a monitor task, the delegator of the monitor task being an owner of the monitor task.
[0026] As an embodiment, the first processor closes the monitor task when the delegated task is completed.
[0027] As an embodiment, the second processor additionally grants the right of reading other tasks relevant to the delegated task to the delegatee.
[0028] As an embodiment, the first processor sets the delegated task to be read-only relative to the delegator, and sets the right of access so that the subordinate task cannot be accessed by the delegator.
[0029] As an embodiment, the workflow management system further comprises a mail transmission device configured to send a notification mail message to the delegator when the delegation is accepted or rejected, the delegated task is completed or deleted, or a due date is changed.
[0030] As an embodiment, the task receiving device receives a task to be delegated through a task list screen when a task delegation button corresponding to said task is pressed on the task list screen.
[0031] As an embodiment, the delegatee receiving device receives a user as the delegatee through a delegatee selection screen when a delegatee selection button corresponding to the user is pressed on the delegatee selection screen.
[0032] As an embodiment, the acceptance receiving device receives the acceptance of the delegation when an acceptance button is pressed on a task list screen or a task details screen, and receives declination of the delegation when a declination button is pressed on the task list screen or the task details screen.
[0033] According to a second aspect of the present invention, there is provided a workflow management method for managing a workflow including a plurality of hierarchically-classified tasks, comprising:
[0034] a task receiving step of receiving designation of a task to be delegated;
[0035] a delegatee receiving step of receiving designation of a delegatee;
[0036] an acceptance receiving step of receiving acceptance of a delegation from the delegatee;
[0037] a first processing step of allowing a delegator to hide a delegated task and a subordinate task, and allowing the delegator to confirm the status of the designated task; and
[0038] a second processing step of allowing the delegator to refer to other tasks relevant to the delegated tasks.
[0039] According to a third aspect of the present invention, there is provided
[0040] 19 . A workflow management device for managing a workflow including a plurality of hierarchically-classified tasks, comprising:
[0041] a task receiving unit configured to receive designation of a task to be delegated;
[0042] a delegatee receiving unit configured to receive designation of a delegatee;
[0043] an acceptance receiving unit configured to receive, from the delegatee, acceptance of a delegation;
[0044] a first processor that allows a delegator to hide a delegated task and a subordinate task, and allows the delegator to confirm status of the designated task; and
[0045] a second processor that allows the delegator to refer to other tasks relevant to the delegated tasks.
[0046] According to the present invention, it is possible to provide a workflow management system suitable for cooperative work spread over different organizations while employing the AKW model or other models.
[0047] These and other objects, features, and advantages of the present invention will become more apparent from the following detailed description of preferred embodiments given with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0048] FIG. 1A and FIG. 1B are block diagrams illustrating a workflow model in the related art;
[0049] FIG. 2 is a block diagram illustrating a configuration of a workflow management system according to an embodiment of the present invention;
[0050] FIG. 3 is a table illustrating a data structure of the tasks managed by the task database 109 ;
[0051] FIG. 4 is a table illustrating a data structure of the task-monitor association table 108 ;
[0052] FIG. 5A and FIG. 5B are block diagrams illustrating the concept of a task delegation;
[0053] FIG. 6 is a sequence diagram illustrating operations on a task list screen on the delegator side;
[0054] FIG. 7 is a flowchart illustrating the operations in step S 105 , in which the task management tool 101 displays the task list screen;
[0055] FIG. 8 is a schematic diagram exemplifying a task list screen 401 ;
[0056] FIG. 9 is a sequence diagram illustrating operations of task delegation;
[0057] FIG. 10 is a schematic diagram exemplifying a delegatee selection screen 411 ;
[0058] FIG. 11 is a table illustrating a data structure of the tasks before delegation;
[0059] FIG. 12 is a block diagram illustrating the structure of the tasks before delegation;
[0060] FIG. 13 is a flow chart illustrating operations of step S 137 in FIG. 9 for creating a monitor task;
[0061] FIG. 14 is a flow chart illustrating operations of step S 140 in FIG. 9 for changing the owner of the delegated task;
[0062] FIG. 15A is a table exemplifying data of the delegated task after delegation;
[0063] FIG. 15B is a table exemplifying data of the delegated task after delegation;
[0064] FIG. 16 is a block diagram illustrating the structure of the tasks after delegation;
[0065] FIG. 17 is a schematic diagram exemplifying a task list screen 421 after delegation on the side of the delegator;
[0066] FIG. 18 is a schematic diagram exemplifying a task list screen 431 after the delegation is finished;
[0067] FIG. 19A is a schematic diagram exemplifying a task list screen 501 on the side of the delegate;
[0068] FIG. 19B is a schematic diagram exemplifying a task details screen 505 ;
[0069] FIG. 20 is a sequence diagram illustrating operations of delegation acceptance;
[0070] FIG. 21A is a table exemplifying data of the delegated task before delegation acceptance;
[0071] FIG. 21B is a table exemplifying data of the delegated task before delegation acceptance;
[0072] FIG. 22 is a block diagram illustrating the structure of the tasks before delegation acceptance.
[0073] FIG. 23 is a flowchart illustrating operations of delegation acceptance;
[0074] FIG. 24A and FIG. 24B are flowcharts illustrating operations of modifying access right;
[0075] FIG. 25A is a table exemplifying data of the delegated task after delegation acceptance;
[0076] FIG. 25B is a table exemplifying data of the delegated task after delegation acceptance;
[0077] FIG. 26 is a block diagram illustrating the structure of the tasks after delegation acceptance;
[0078] FIG. 27 is a schematic diagram exemplifying a task details screen 511 on the delegate side after delegation acceptance;
[0079] FIG. 28 is a sequence diagram illustrating operations of delegation declination;
[0080] FIG. 29A is a table exemplifying data of the delegated task before delegation declination;
[0081] FIG. 29B is a table exemplifying data of the monitor task before delegation declination;
[0082] FIG. 30 is a block diagram illustrating the structure of the tasks before delegation declination;
[0083] FIG. 31 is a flowchart illustrating operations of delegation declination;
[0084] FIG. 32A is a table exemplifying data of the delegated task after delegation declination;
[0085] FIG. 32B is a table exemplifying data of the monitor task after delegation declination;
[0086] FIG. 33 is a block diagram illustrating the structure of the tasks after delegation declination;
[0087] FIG. 34 is a sequence diagram illustrating operations of delegated task completion and task attribute modification;
[0088] FIG. 35 is a flowchart illustrating operations after task status modification;
[0089] FIG. 36A is a table exemplifying data of the delegated task after the delegated task is completed; and
[0090] FIG. 36B is a table exemplifying data of the monitor task after the delegated task is completed.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0091] Below, preferred embodiments of the present invention are explained with reference to the accompanying drawings.
[0000] System Configuration
[0092] FIG. 2 is a block diagram illustrating a configuration of a workflow management system according to an embodiment of the present invention.
[0093] The workflow management system as shown in FIG. 2 includes a management server 100 located on a network, a browser 201 and a mail reader 301 , which are operated by a delegator U 1 , and can be connected to the management server 100 through a network, and a browser 202 and a mail reader 302 , which are operated by a delegatee U 2 , and can be connected to the management server 100 through a network.
[0094] The management server 100 includes a task management tool 101 , which serves as a front-end for the browsers 201 , 202 , a workflow engine 102 for workflow control, a number of databases (DB) 108 through 110 , and an SMTP (Simple Mail Transfer Protocol) server 111 for mail notification.
[0095] The databases 108 through 110 include a task-monitor association table 108 , which manages the association relationships between tasks constituting the workflow and monitor tasks for monitoring delegated tasks; a task database 109 , which manages task information; and an organization database 110 , which manages data of the organizations to which operators of the workflow belong.
[0096] The workflow engine 102 includes a notification mail generator 103 , which creates notification mail for the SMTP server 111 ; a task-monitor association table manager 104 , which manages the task-monitor association table 108 ; a task attribute manager 105 , which manages task attributes; a task access right manager 106 , which manages the right to access the tasks; and an organization data manager 107 , which manages the organization data.
[0097] FIG. 3 is a table illustrating a data structure of the tasks managed by the task database 109 .
[0098] As shown in FIG. 3 , the data structure of the tasks under management includes columns of “attribute name”, “attribute value (examples)”, and “remarks”.
[0099] For example, the column of “attribute name” includes items of “task ID”, “task name”, “parent task ID”, “child task ID”, “preceding task ID”, “task status”, “task owner”, “due date”, “completion date”, “new task”, “relevant information item ID”, “monitor task ?”, “delegated task ?”, “task-monitor association ID”, “comment”, and “read access right holder”.
[0100] The column of “attribute value” contains values of the items in the column of “attribute name”. For example, in FIG. 3 , the attribute value of “task ID” is “ 10010 ”, that of “task name” is “review a specification”, that of “parent task ID” is “ 9822 ”, that of “child task ID” is “ 10011 ”, “ 10012 ”, that of “preceding task ID” is “ 10003 ”, that of “task status” is “processible”, that of “task owner” is “Maeda”, that of “due date” is “2005/03/22”, that of “completion date” is “null”, that of “new task” is “false”, that of “relevant information item ID” is “ 3022 ”, “ 3033 ”, that of “monitor task ?” is “false”, that of “delegated task ?” is “false”, that of “task-monitor association ID” is “null”, that of “comment” is “null”, and that of “read access right holder” is “null”.
[0101] The column of “remarks” contains explanation of the items in the column of “attribute name”. For example, in FIG. 3 , the remarks of “task ID” is “uniquely identified ID”, that of “parent task ID” is “task ID of parent task or null”, that of “child task ID” is “list of task ID of child tasks (might be empty)”, that of “preceding task ID” is “list of task ID of preceding tasks (might be empty)”, that of “task status” is “one of processible, waiting for preceding task, finished, in work, waiting for completion, declination, invisible”, that of “task owner” is “user ID (singular)”, that of “due date” is “date”, that of “completion date” is “date when task is completed or null”, of “new task” is “truth value”, that of “relevant information item ID” is “ID of relevant information project”, that of “monitor task ?” is “truth value”, that of “delegated task ?” is “truth value”, that of “task-monitor association ID” is “ID of task-monitor association table or null”, that of “comment” is “character string value”, and that of “read access right holder” is “IDs of users (plural) allowed to read other than owner”.
[0102] FIG. 4 is a table illustrating a data structure of the task-monitor association table 108 .
[0103] As shown in FIG. 4 , the task-monitor association table 108 includes columns of “attribute name”, “attribute value (examples)”, and “remarks”.
[0104] For example, the column of “attribute name” includes items of “task-monitor association ID”, “task ID of delegated task”, “task ID of monitor task”, “delegator user”, “delegatee user”, “mail notification of delegation acceptance”, “mail notification of delegation declination”, “mail notification of completion”, “mail notification of deletion”, and “mail notification of date change”.
[0105] The column of “attribute value” contains values of the items in the column of “attribute name”.
[0106] The column of “remarks” contains explanation of the items in the column of “attribute name”. For example, in FIG. 4 , the remarks of “task-monitor association ID” is “uniquely identified ID”, that of “ID of delegated task” is “task ID of task to be delegated”, that of “ID of monitor task” is “task ID of corresponding monitor task”, that of “delegator user” is “user ID of user making delegation”, that of “delegates user” “user ID of user requested by delegator user”, that of “mail notification of delegation acceptance” is “mail notification to delegator user at the time of delegation acceptance (truth value)”, that of “mail notification of delegation declination” is “mail notification to delegator user at the time of delegation declination”, that of “mail notification of completion” is “mail notification to delegator user at the time of task completion”, that of “mail notification of deletion” is “mail notification to delegator user at the time of task deletion”, and that of “mail notification of date change” is “mail notification to delegator user when changing delivery date”.
[0000] Concept of Task Delegation
[0107] FIG. 5A and FIG. 5B are block diagrams illustrating the concept of a task delegation.
[0108] Specifically, FIG. 5A illustrates a state before the task delegation, and FIG. 5B illustrates a state after the task delegation.
[0109] As shown in FIG. 5A , before the task delegation, owners of tasks T 1 through T 10 are a user A, and only the user A is allowed to access the tasks T 1 through T 10 ; under this condition, the user A delegates the task T 7 to a user B.
[0110] In this case, as shown in FIG. 5B , because of an owner change, the task T 7 and its subordinate tasks T 9 , T 10 can only be accessed by the user B, and a monitor task MT for monitoring the status of the task T 7 is created, and the monitor task MT can be accessed only by the user A, who is a delegator. The preceding tasks and parent tasks of the delegated task T 7 , that is, tasks T 1 , T 3 , T 4 , T 6 , can be accessed by both the user A and the user B.
[0111] In this way, the task T 7 can completely determine completion or not, or other conditions of the delegated task T 7 ; the user B, who executes the task 7 , can obtain necessary information from the preceding tasks and parent tasks of the task T 7 , and can hide details of the information from the user A.
[0000] Processing on Delegator Side
[0112] FIG. 6 is a sequence diagram illustrating operations on a task list screen on the delegator side.
[0113] As shown in FIG. 6 , in step S 101 , from the browser 201 of the delegator U 1 , a request to view a task list is made to the task management tool 101 of the management server 100 .
[0114] In step S 102 and step S 103 , the task management tool 101 obtains task information from the workflow engine 102 .
[0115] In step S 104 , the task management tool 101 creates the task list screen data.
[0116] In step S 105 , the task management tool 101 displays the task list on a screen.
[0117] In step S 106 , the task management tool 101 sends data of the task list screen to the browser 201 of the delegator U 1 , and the task list is displayed by the browser 201 .
[0118] FIG. 7 is a flowchart illustrating the operations in step S 105 , in which the task management tool 101 displays the task list screen.
[0119] As shown in FIG. 7 , in step Sill, an “id” is specified to start the routine of displaying the task list screen.
[0120] In step S 112 , a task having a task ID equaling the specified “id” is acquired.
[0121] In step S 113 , it is determined whether the task status is invisible. If the task status is invisible, the routine ends in step S 121 . Otherwise, the routine proceeds to step S 114 .
[0122] In step S 114 , a task name, a due date, and other bibliographic information are displayed.
[0123] In step S 115 , it is determined whether parent tasks include a task in work.
[0124] If there is a task in work, the routine ends in step S 121 , otherwise, the routine proceeds to step S 116 .
[0125] In step S 116 , it is determined whether the task is a monitor task. If the task is a monitor task, the routine proceeds to step S 117 , otherwise, the routine proceeds to step S 118 .
[0126] In step S 117 , an arrow icon representing the monitor task is displayed.
[0127] In step S 118 , it is determined whether the task status is “in work”. If the task status is “in work”, the routine proceeds to step S 120 , otherwise, the routine proceeds to step S 119 .
[0128] In step Sl 19 , operational buttons for sub tasks addition, tasks deletion, and tasks delegation are displayed. Then, the routine ends in step S 121 .
[0129] In step S 120 , operational buttons for accepting or declining the delegated task are displayed. Then, the routine ends in step S 121 .
[0130] FIG. 8 is a schematic diagram exemplifying a task list screen 401 .
[0131] As show in FIG. 8 , task delegation buttons 403 are shown on the right side of a task list 402 .
[0132] FIG. 9 is a sequence diagram illustrating operations of task delegation.
[0133] As shown in FIG. 9 , in step S 131 , when a task delegation button 403 is pressed on the task list screen 401 on the browser 201 of the delegator U 1 , this action is reported to the task management tool 101 .
[0134] In step S 132 and step S 133 , the task management tool 101 requests organization information from the workflow engine 102 .
[0135] In step S 134 , a delegatee selection screen including task names and organization information is displayed.
[0136] In step S 135 , the delegator U 1 selects a delegatee from the delegatee selection screen on the browser 201 of the delegator U 1 .
[0137] In step S 136 , the task management tool 101 sends a request for task delegation to the workflow engine 102 .
[0138] In step S 137 , the workflow engine 102 creates a monitor task.
[0139] In step S 138 , a monitor task ID is returned to the task management tool 101 .
[0140] In step S 139 , the task management tool 101 notifies the browser 201 of the delegator U 1 of the results.
[0141] In step S 140 , the workflow engine 102 changes the owner of the delegated task.
[0142] In step S 141 , the workflow engine 102 requests the SMTP server 111 to send a notification mail.
[0143] In step S 142 , the SMTP server 111 sends the mail to the mail reader 302 of the delegatee U 2 .
[0144] FIG. 10 is a schematic diagram exemplifying a delegatee selection screen 411 .
[0145] As show in FIG. 10 , there are delegatee selection buttons 412 , task information 413 , mail notification setting check boxes 414 , and a delegatee assigning button 415 on the delegatee selection screen 411 .
[0146] FIG. 11 is a table illustrating a data structure of the tasks before delegation.
[0147] FIG. 12 is a block diagram illustrating the structure of the tasks before delegation.
[0148] Here, the delegated task is the task indicated by a thick frame and has a task ID of 10010 .
[0149] FIG. 13 is a flow chart illustrating operations of step S 137 in FIG. 9 for creating a monitor task.
[0150] As shown in FIG. 13 , in step S 151 , the routine of monitor task creation is started.
[0151] In step S 152 , the delegated task is duplicated, and a new task is created to be the monitor task.
[0152] In step S 153 , a new task ID is assigned to the monitor task.
[0153] In step S 154 , attributes of the monitor task are changed. Specifically, the “task status” is changed to be “in work”, the “monitor task ?” is changed to be “true”, the “child task ID” is changed to be “null”, and the “preceding task ID” is changed to be “null”.
[0154] In step S 155 , attributes of the delegated task are changed. Specifically, the “task status” is changed to be “in work”, the “delegated task ?” is changed to be “true”, and the “new task” is changed to be “true”.
[0155] In step S 156 , a task-monitor association table object is created.
[0156] In step S 157 , attributes of the task-monitor association table are set from information input to the delegatee selection screen.
[0157] In step S 158 , an association table ID is assigned to the delegated task and the monitor task.
[0158] In step S 159 , the routine ends.
[0159] FIG. 14 is a flow chart illustrating operations of step S 140 in FIG. 9 for changing the owner of the delegated task.
[0160] As shown in FIG. 14 , in step S 161 , the routine of changing the task owner is started.
[0161] In step S 162 , the owner of the task having the task ID equaling “id” is regarded as the task owner.
[0162] In step S 163 , a list of the child task ID is given to “children”.
[0163] In step S 164 , it is determined whether “children” is an empty list. If “children” is an empty list, the routine ends in step S 167 . Otherwise, the routine proceeds to step S 165 .
[0164] In step S 165 , the first element of “children” is given to “cid”, and the rest of the list remains in “children”.
[0165] In step S 166 , a procedure of changing the task owner is invoked self-recursively. Then, the routine returns to step S 164 to determine whether “children” is an empty list. This routine stops in step S 167 when “children” becomes an empty list.
[0166] FIG. 15A is a table exemplifying data of the delegated task after delegation.
[0167] FIG. 15B is a table exemplifying data of the delegated task after delegation.
[0168] In FIG. 15A and FIG. 15B , the shaded fields are modified.
[0169] FIG. 16 is a block diagram illustrating the structure of the tasks after delegation.
[0170] In FIG. 16 , owners of a delegated task (task ID: 10010 ) and child tasks (task ID: 10011 , 10012 ) are changed, and a monitor task (task ID: 10032 ) is created, the delegated task (task ID: 10010 ) and the monitor task (task ID: 10032 ) are associated through an object of the task monitor association table (task monitor association ID: 1011 ).
[0171] FIG. 17 is a schematic diagram exemplifying a task list screen 421 after delegation on the side of the delegator.
[0172] As show in FIG. 17 , a symbol 422 indicates a delegated task is a monitor task, and a symbol 423 indicates a status of “delegated”.
[0173] FIG. 18 is a schematic diagram exemplifying a task list screen 431 after the delegation is finished.
[0174] In FIG. 18 , only the monitor tasks are selected for illustration.
[0000] Processing on Side of Delegatee
[0175] FIG. 19A is a schematic diagram exemplifying a task list screen 501 on the side of the delegatee.
[0176] FIG. 19B is a schematic diagram exemplifying a task details screen 505 .
[0177] In FIG. 19A , for the delegated task, an accept button 503 and a decline button 504 are displayed on a task list 502 of the task list screen 501 . In FIG. 19B , an accept button 506 and a decline button 507 are displayed on the task details screen 505 , and a symbol 508 is shown to indicate a status of “delegated”.
[0178] FIG. 20 is a sequence diagram illustrating operations of delegation acceptance.
[0179] As shown in FIG. 20 , in step S 201 , the delegatee U 2 presses a delegation acceptance button on the task list screen on the browser 202 of the delegatee U 2 .
[0180] In step S 202 , the task management tool 101 requests the workflow engine 102 to accept the delegation.
[0181] In step S 203 , as one step of accepting the delegation, the workflow engine 102 modifies task attributes.
[0182] In step S 204 , the workflow engine 102 modifies the access right.
[0183] In step S 205 , the workflow engine 102 notifies the task management tool 101 of the modified task attributes.
[0184] In step S 206 , the task management tool 101 reports the results to the browser 202 of the delegatee U 2 .
[0185] In step S 207 , the workflow engine 102 requests the SMTP server 111 to send a notification mail message.
[0186] In step S 208 , the SMTP server 111 sends the mail message to the mail reader 301 of the delegator U 1 .
[0187] FIG. 21A is a table exemplifying data of the delegated task before delegation acceptance.
[0188] FIG. 21B is a table exemplifying data of the delegated task before delegation acceptance.
[0189] FIG. 22 is a block diagram illustrating the structure of the tasks before delegation acceptance.
[0190] FIG. 23 is a flowchart illustrating operations of delegation acceptance.
[0191] As shown in FIG. 23 , in step S 211 , the routine of delegation acceptance is started.
[0192] In step S 212 , an association table is obtained from an association table ID of the delegated task.
[0193] In step S 213 , a monitor task is obtained from a monitor task ID of the association table.
[0194] In step S 214 , attributes of the delegated task are modified. Specifically, the “task status” is modified to be “processible”, and the “new task” is changed to be “false”.
[0195] In step S 215 , attributes of the monitor task are modified. Specifically, the “task status” is modified to be “waiting for completion”.
[0196] In step S 216 , the access right is modified, such as, the task ID of the delegated task, and the user ID of the delegate.
[0197] In step S 217 , it is determined whether a notification is required when the delegation is accepted. If the notification is required, the routine proceeds to step S 218 , otherwise, to step S 219 to complete the routine.
[0198] In step S 218 , a notification mail message is sent to the delegator U 1 .
[0199] In step S 219 , the routine ends.
[0200] FIG. 24A and FIG. 24B are flowcharts illustrating operations of modifying access right.
[0201] Specifically, FIG. 24A illustrates operations of modifying the access right, and FIG. 24B illustrates operations of setting the access right of a preceding task in FIG. 24A .
[0202] As shown in FIG. 24A , in step S 221 , the routine of access right modification is started by specifying “id” and “user”.
[0203] In step S 222 , a task having a task ID equaling “id” is obtained.
[0204] In step S 223 , a list of the child task ID is given to “children”.
[0205] In step S 224 , it is determined whether “children” is an empty list. If “children” is an empty list, the routine proceeds to step S 227 . Otherwise, the routine proceeds to step S 225 .
[0206] In step S 225 , the first element of “children” is given to “cid”, and the rest of the list remains in “children”.
[0207] In step S 226 , the access right of the preceding task is set by specifying “cid” and “user”.
[0208] In step S 227 , when “children” becomes an empty list, it is determined whether the parent task ID is null. If the parent task ID is null, the routine proceeds to step S 232 , otherwise, the routine proceeds to step S 228 .
[0209] In step S 228 , the parent task ID is given to “id”.
[0210] In step S 229 , a task having a task ID equaling “id” is obtained.
[0211] In step S 230 , “user” is added to be a read-access right holder.
[0212] In step S 231 , the access right of the preceding task is set by using “cid” and “user”, and the routine returns to step S 227 to determine whether the parent task ID is null.
[0213] In step S 232 , when the parent task ID becomes null, the routine ends.
[0214] As shown in FIG. 24B , in step S 241 , the routine of setting the access right of the preceding task by specifying “id” and “user” is started.
[0215] In step S 242 , a task having a task ID equaling “id” is obtained.
[0216] In step S 243 , a list of the preceding task ID is given to “preds”.
[0217] In step S 244 , it is determined whether “preds” is an empty list. If “preds” is an empty list, the routine proceeds to step S 248 , otherwise, the routine proceeds to step S 245 .
[0218] In step S 245 , the first element of “preds” is given to “predid”, and the rest of the list remains in “preds”.
[0219] In step S 246 , a task having a task ID equaling “predid” is obtained. This task is referred to as “pred_task”.
[0220] In step S 247 , “user” is added as a read access-right holder of the pred_task, and the routine returns to step S 244 to determine whether the “preds” is an empty list.
[0221] In step S 248 , when the “preds” becomes an empty list, the routine ends.
[0222] FIG. 25A is a table exemplifying data of the delegated task after delegation acceptance.
[0223] FIG. 25B is a table exemplifying data of the delegated task after delegation acceptance.
[0224] In FIG. 25A and FIG. 25B , the shaded fields are modified.
[0225] FIG. 26 is a block diagram illustrating the structure of the tasks after delegation acceptance.
[0226] In FIG. 26 , the preceding tasks and the parent task are accessible, the delegatee is additionally granted access right of reading tasks having task IDs 9810 , 10003 , 7121 , and 9822 .
[0227] FIG. 27 is a schematic diagram exemplifying a task details screen 511 on the delegate side after delegation acceptance.
[0228] FIG. 28 is a sequence diagram illustrating operations of delegation declination.
[0229] As shown in FIG. 28 , in step S 251 , the delegatee U 2 presses a delegation declination button on the task list screen on the browser 202 of the delegatee U 2 .
[0230] In step S 252 , the task management tool 101 requests the workflow engine 102 to decline the delegation.
[0231] In step S 253 , as one step of declining the delegation, the workflow engine 102 modifies the task attributes.
[0232] In step S 254 , the workflow engine 102 modifies the task owner.
[0233] In step S 255 , the workflow engine 102 notifies the task management tool 101 of completion of the routine.
[0234] In step S 256 , the task management tool 101 reports the results to the browser 202 of the delegatee U 2 .
[0235] In step S 257 , the workflow engine 102 requests the SMTP server 111 to send a notification mail message.
[0236] In step S 258 , the SMTP server 111 sends the mail message to the mail reader 301 of the delegator U 1 .
[0237] FIG. 29A is a table exemplifying data of the delegated task before delegation declination.
[0238] FIG. 29B is a table exemplifying data of the monitor task before delegation declination.
[0239] FIG. 30 is a block diagram illustrating the structure of the tasks before delegation declination.
[0240] FIG. 31 is a flowchart illustrating operations of delegation declination.
[0241] As shown in FIG. 31 , in step S 261 , the routine of delegation declination is started.
[0242] In step S 262 , an association table is obtained from an association table ID of the delegated task.
[0243] In step S 263 , a monitor task is obtained from a monitor task ID of the association table.
[0244] In step S 264 , attributes of the delegated task are modified. Specifically, the “task status” is modified to be “declined”, the “new task” is modified to be “false”, the “delegated task ?” is modified to be “false”, the “task-monitor association table ID” is modified to be “null”.
[0245] In step S 265 , attributes of the monitor task are modified. Specifically, the “task status” is modified to be “invisible”.
[0246] In step S 266 , the task owner is modified.
[0247] In step S 267 , it is determined whether a notification is required when the delegation is of declined. If a notification is required, the routine proceeds to step S 268 , otherwise, to step S 269 to end the routine.
[0248] In step S 268 , a notification mail message is sent to the delegator U 1 .
[0249] In step S 269 , the routine ends.
[0250] FIG. 32A is a table exemplifying data of the delegated task after delegation declination.
[0251] FIG. 32B is a table exemplifying data of the monitor task after delegation declination.
[0252] In FIG. 32A and FIG. 32B , the shaded fields are modified.
[0253] FIG. 33 is a block diagram illustrating the structure of the tasks after delegation declination.
[0254] In FIG. 33 , owners of the declined task (task ID: 10010 ) and its children tasks (task ID: 10011 , 10012 ) are modified to be the original delegator, and the monitor task (task ID: 10032 ) is set to be invisible.
[0255] FIG. 34 is a sequence diagram illustrating operations of delegated task completion and task attribute modification.
[0256] As shown in FIG. 34 , in step S 271 , the delegatee U 2 inputs task completion from the task list screen on the browser 202 of the delegatee U 2 .
[0257] In step S 272 , the task management tool 101 requests the workflow engine 102 to modify the task attributes.
[0258] In step S 273 , the workflow engine 102 modifies the task attributes.
[0259] In step S 274 , the workflow engine 102 notified the task management tool 101 of the modified task attributes.
[0260] In step S 275 , the task management tool 101 presents the results in the browser 202 .
[0261] In step S 276 , the workflow engine 102 performs operations after task status modification.
[0262] In step S 277 , the workflow engine 102 requests the SMTP server 111 to send a notification mail message.
[0263] In step S 278 , the SMTP server 111 sends the mail message to the mail reader 301 of the delegator U 1 .
[0264] FIG. 35 is a flowchart illustrating operations after task status modification.
[0265] As shown in FIG. 35 , in step S 281 , the routine after task status modification is started.
[0266] In step S 282 , it is determined whether the task under processing is a delegated task. If it is a delegated task, the routine proceeds to step S 283 , otherwise, to step S 290 to end the routine.
[0267] In step S 283 , an association table is obtained from an association table ID of the delegated task.
[0268] In step S 284 , a monitor task is obtained from a monitor task ID of the association table.
[0269] In step S 285 , attributes of the delegated task, such as, “due date”, “completion date”, “comment”, are duplicated to the monitor task.
[0270] In step S 286 , it is determined whether attributes of the notification object are to be modified. If the attributes are to be modified, the routine proceeds to step S 287 , otherwise, to step S 288 .
[0271] In step S 287 , a notification mail message is sent to the delegator.
[0272] In step S 288 , it is determined whether the delegated task is completed. If the delegated task is completed, the routine proceeds to step S 289 , otherwise, to step S 290 to end the routine.
[0273] In step S 289 , attributes of the monitor task are modified. Specifically, the “task status” is modified to be “completed”.
[0274] In step S 290 , the routine ends.
[0275] FIG. 36A is a table exemplifying data of the delegated task after the delegated task is completed.
[0276] FIG. 36B is a table exemplifying data of the monitor task after the delegated task is completed.
[0277] In FIG. 36A and FIG. 36B , the shaded fields In FIG. 36A are duplicated to the monitor task.
[0000] Another Method of Implementing Task Monitoring
[0278] In the above embodiments, it is described that the monitor task monitors the delegated tasks. However, monitoring the delegated tasks can also be controlled by only the access right of the same object without creating the monitor task. In this case, for example, as to the subordinate task, the right of reading and editing is granted, and the right of access is granted when delegating or accepting the task (specifically, it can be set that the delegator can only read the delegated task, and the delegator cannot access the subordinate tasks), it is possible to monitor the delegated tasks.
[0279] Compared to monitoring the delegated task by control of the access rights, the above-described method of monitoring the delegated task by the monitor task has the following advantages.
[0280] (1) It is possible to hide attribute modification of the delegated task (disclosed only at the time of completion), because for the same object, it is possible to refer successively. However, setting the right of access in units of attributes is cumbersome.
[0281] (2) Setting the right of access of the objects (child task and relevant information), which are to be added to the delegated task, is simple, while setting the right of access of the child tasks to be added is difficult.
[0282] While the present invention is described with reference to specific embodiments chosen for purpose of illustration, it should be apparent that the invention is not limited to these embodiments, but numerous modifications could be made thereto by those skilled in the art without departing from the basic concept and scope of the invention.
[0283] This patent application is based on Japanese Priority Patent Application No. 2006-003497 filed on Jan. 11, 2006, the entire contents of which are hereby incorporated by reference. | A workflow management system is disclosed that is suitable to manage a workflow including plural hierarchically-classified tasks and especially for cooperative work spread over different organizations. The workflow management system includes a task receiving unit to receive designation of a task to be delegated, a delegatee receiving unit to receive designation of a delegatee, an acceptance receiving unit to receive acceptance of a delegation from the delegatee, a first processor that allows a delegator to hide a delegated task and a subordinate task, and allows the delegator to confirm status of the designated task, and a second processor that allows the delegator to refer to other tasks relevant to the delegated tasks. | 6 |
[0001] This application claims priority under 35 U.S.C. §119(e) to provisional patent application No. 60/176,884, filed Jan. 19, 2000 and provisional patent application No. 60/251,759, filed Dec. 7, 2000.
US GOVERNMENT RIGHTS
[0002] This invention was made with United States Government support under Grant No. HD U54 29099, awarded by the National Institutes of Health. The United States Government has certain rights in the invention.
FIELD OF THE INVENTION
[0003] The present invention is directed to directed to two novel, testis-specific proteins, designated C19 and C23. These proteins have been designated lysozyme paralogues due to their high degree of conservation of critical amino acids found in other lysozyme-C's.
BACKGROUND OF THE INVENTION
[0004] Lysozymes are hydrolases capable of lysing many bacteria. They cleave a beta-glycosidic bond between the C-1 of N-acetylmuramic acid and the C-4 of N-acetylglucosamine of the bacterial cell wall peptidoglycans (murein). Besides this muraindase activity they also display some chitinase (fungal cell wall component) activity. Lysozymes also are credited with antibacterial and antiviral capacities different from the bacteriolytic activity. For example, lysozymes have been demonstrated to have HIV 1 antiviral activity.
[0005] Lysozymes have been found in many biological tissues and secretions. Stomach lysozymes (cow, leaf-eating monkey) are even specialized to function at lower pH. There are two types of lysozymes found in the animal kingdom: C-type or chicken-type lysozymes represented by chicken egg white lysozyme, and G-type or goose type lysozymes represented by goose-egg white lysozyme. The C-type lysozymes are actually considered a superfamily including conventional lysozymes, calcium-binding lysozymes, and alpha-lactalbumins. All lysozymes have very similar tertiary structures, but vary in amino-acid composition.
[0006] Only one lysozyme has been identified and cloned from human tissues and body fluids. The gene coding for the human lysozyme is located on chromosome 12. A second lysozyme C gene was found on chromosome 17, but the corresponding protein has not been described (H. Nomiyama, J of Interferon and Cytokine Research 19: 227, 1999). Lysozyme C is a gene of 5856 bp and comprises four exons. The encoded protein is a secretory protein and comprises an 18 amino acid signal sequence and a mature protein of 130 residues. The mature protein contains four disulfide bonds between Cys 6—Cys 128, Cys 30—Cys 116, Cys 65—Cys 81, and Cys 77—Cys 95. This protein has been isolated from placenta, amniotic fluid, milk, tears, intestinal cells and leucocytes.
[0007] The present invention is directed to two human sperm proteins that have recently been isolated (C19 and C23) and appear to be lysozyme-C paralogues. These proteins are expressed specifically in sperm cell and are believed to function in the events relating to sperm/egg fussion and fertilization.
[0008] Definitions
[0009] In describing and claiming the invention, the following terminology will be used in accordance with the definitions set forth below.
[0010] As used herein, “nucleic acid,” “DNA,” and similar terms also include nucleic acid analogs, i.e. analogs having other than a phosphodiester backbone. For example, the so-called “peptide nucleic acids,” which are known in the art and have peptide bonds instead of phosphodiester bonds in the backbone, are considered within the scope of the present invention.
[0011] The term “peptide” encompasses a sequence of 3 or more amino acids wherein the amino acids are naturally occurring or synthetic (non-naturally occurring) amino acids. Peptide mimetics include peptides having one or more of the following modifications:
[0012] 1. peptides wherein one or more of the peptidyl —C(O)NR— linkages (bonds) have been replaced by a non-peptidyl linkage such as a —CH 2 — carbamate linkage (—CH 2 OC(O)NR—), a phosphonate linkage, a —CH 2 —sulfonamide (—CH 2 —S(O) 2 NR—) linkage, a urea (—NHC(O)NH—) linkage, a —CH 2 — secondary amine linlage, or with an alkylated peptidyl linkage (—C(O)NR—) wherein R is C 1 -C 4 alkyl;
[0013] 2. peptides wherein the N-terminus is derivatized to a —NRR 1 group, to a —NRC(O)R group, to a —NRC(O)OR group, to a —NRS(O) 2 R group, to a —NHC(O)NHR group where R and R 1 are hydrogen or C 1 -C 4 alkyl with the proviso that R and R 1 are not both hydrogen;
[0014] 3. peptides wherein the C terminus is derivatized to —C(O)R 2 where R 2 is selected from the group consisting of C 1 -C 4 alkoxy, and —NR 3 R 4 where R 3 and R 4 are independently selected from the group consisting of hydrogen and C 1 -C 4 alkyl.
[0015] Naturally occurring amino acid residues in peptides are abbreviated as recommended by the IUPAC-IUB Biochemical Nomenclature Commission as follows: Phenylalanine is Phe or F; Leucine is Leu or L; Isoleucine is Ile or I; Methionine is Met or M; Norleucine is NMe; Valine is Vat or V; Serine is Ser or S; Proline is Pro or P; Threonine is Thr or T; Alanine is Ala or A; Tyrosine is Tyr or Y; Histidine is His or H; Glutamine is Ghn or Q; Asparagine is Asn or N; Lysine is Lys or K; Aspartic Acid is Asp or D; Glutamic Acid is Glu or E; Cysteine is Cys or C; Tryptophan is Trp or W; Arginine is Arg or R; Glycine is Gly or G, and X is any amino acid. Other naturally occurring amino acids include, by way of example, 4-hydroxyproline, 5-hydroxylysine, and the like.
[0016] Synthetic or non-naturally occurring amino acids refer to amino acids which do not naturally occur in vivo but which, nevertheless, can be incorporated into the peptide structures described herein. The resulting “synthetic peptide” contain amino acids other than the 20 naturally occurring, genetically encoded amino acids at one, two, or more positions of the peptides. For instance, naphthylalanine can be substituted for trytophan to facilitate synthesis. Other synthetic amino acids that can be substituted into peptides include L-hydroxypropyl, L-3,4-dihydroxyphenylalanyl, alpha-amino acids such as L-alpha-hydroxylysyl and D-alpha-methylalanyl, L-alpha.-methylalanyl, beta.-amnino acids, and isoquinolyl D amino acids and non-naturally occurring synthetic amino acids can also be incorporated into the peptides. Other derivatives include replacement of the naturally occurring side chains of the 20 genetically encoded amino acids (or any L or D amino acid) with other side chains.
[0017] As used herein, the term “conservative amino acid substitution” are defincd herein as exchanges within one of the following five groups:
[0018] I. Small aliphatic, nonpolar or slightly polar residues:
[0019] Ala, Ser, Thr, Pro, Gly;
[0020] II. Polar, negatively charged residues and their amides:
[0021] Asp, Asn, Gl, Gln;
[0022] IfI. Polar, positively charged residues:
[0023] His, Arg, Lys;
[0024] IV. Large, aliphatic, nonpolar residues:
[0025] Met Leu, Ile, Val, Cys
[0026] V. Large, aromatic residues:
[0027] Phe, Tyr, Trp
[0028] As used herein, the term “purified” and like terms relate to the isolation of a molecule or compound in a form that is substantially free of contaminants normally associated with the molecule or compound in a native or natural environment.
[0029] As used herein, the term “Cl 9 polypeptide” and like terms refers to polypeptides comprising SEQ ID NO: 2 and biologically active fragments thereof (such as the mature form represented by SEQ ID NO: 8, for example) and the term “C23 polypeptide” and like terms refers to polypeptides comprising SEQ ID NO: 4 and biologically active fragments thereof (such as the mature form represented by SEQ ID NO: 9, for example).
[0030] As used herein, the term “biologically active fragment” or “bioactive fragment” of a C19 or C23 polypeptide encompasses natural or synthetic portions of SEQ ID NO: 2 or SEQ ID NO: 4, respectively, that are capable of specific binding to at least one of the natural ligands of the respective native polypeptide.
[0031] “Operably linked” refers to ajuxtaposition wherein the components are configured so as to perform their usual function. Thus, control sequences or promoters operably linked to a coding sequence are capable of effecting the expression of the coding sequence.
[0032] As used herein, the term “pharmaceutically acceptable carrier” encompasses any of the standard pharmaceutical carriers, such as a phosphate buffered saline solution, water and emulsions such as an oil/water or water/oil emulsion, and various types of wetting agents.
SUMMARY OF THE INVENTION
[0033] The present invention is directed to two lysozyme-like proteins (C19 and C23), nucleic acid sequences encoding those proteins, and antibodies generated against said proteins. Compositions comprising the native C19 or C23 peptides can be used in contraceptive vaccine formulations. Furthermore, antibodies generated against C19 and C23 can be used as diagnostic agents or can be formulated in compositions that are used to interfere with the binding of sperm cells to oocytes. In one embodiment, the present invention is directed to derivatives of the C19 and C23 proteins that have been modified to have lysozyme activity. These modified proteins can be used in any of the applications that currently use human lysozyme C, including antibacterial and antiviral formulations.
BRIEF DESCRIPTION OF THE DRAWINGS
[0034] [0034]FIGS. 1A and 1B is a copy of a multiple tissue Northern Blot, wherein either C19 cDNA (FIG. 1A) or C23 eDNA (FIG. 11B) was radiolabeled with P 32 and hybridized to 2 ug poly-(A)+ mRNAs, revealing a 1 kb (FIG. 1A) or 0.8 kb (FIG. 1B) message only in testicular RNA. Size of molecular weight markers is indicated at left; lanes 1-8 contain poly-(A)+ MRNA isolated from spleen, thymus, prostate, testis, ovary, small intestine, colon and leucocyte, respectively. The lower panel of FIGS. 1A and 1B shows the identical blot probed with M-actin CDNA as a positive control.
[0035] [0035]FIG. 2 is a comparison of the mature C19 polypeptide with the mature lysozyrne peptides of other species.
[0036] [0036]FIG. 3 is a comparison of the mature C23 polypeptide with the mature lysozynie peptides of other species.
DETAILED DESCRIPTION OF THE INVENTION
[0037] Two human sperm proteins have recently been isolated, C19 and C23, that appear to be lysozyme-C paralogues. These proteins are classified as lysozyme paralogues because of their high degree of conservation of critical amino acids found in other lysozyme-C's. However, they differ significantly from the known human lysozyme-C in nucleic acid and amino acid sequence, and their genes are located on different chromosomes. The new proteins C19 and C23 are approximately 15 kDa with pI's of 5.2 and 5.9, respectively. They possess sequence homology to the known human lysozyme-C; however, C19 and C23 are located on chromosome 17 and the X-chromosome, respectively, and thus these two genes represent new human lysozyme-like genes. The nucleic acid sequence and the deduced amino acid sequence of C19 are represented by SEQ ID NO: 1 and SEQ ID NO: 3, respectively, and nucleic acid sequence and the deduced amino acid sequence of C23 are represented by SEQ ID NO: 2 and SEQ ID NO: 4, respectively.
[0038] C19 and C23 each contain a signal peptide. The initial C19 polypeptide is synthesized as a 215 anino acid polypeptide (SEQ ID NO: 2) having a MW of 23.4 kDaandapof8.0. The mature C19 peptide is 128 amino acids (SEQ ID NO: 8) and has a MW of about 14.6 kDa and pI of 5.0. The initial C23 polypeptide is synthesized as a 159 amino acid polypeptide (SEQ ID NO: 4) having a MW of 17.9 kDa and a pI of 5.9. The mature C23 peptide is 138 amino acids (SEQ ID NO: 9) and has a MW of about 15.7 kDa and pI of 5.9.
[0039] C19 and C23 have 48.8% sequence identity between one another and have 52% and 44% amino-acid sequence identity with the one known mature human lysozyme C, respectively, and 44% and 43% amino-acid sequence identity with the predicted lysozyme homologue on chromosome 17q11.2. C19 is most closely related to human lysozyme (52% sequence identity), whereas C23 is most closely related to chicken lysozyme (51% sequence identity).
[0040] The gene encoding C19 is located on Chromosome 17 and is 6012 bp in length. The C19 gene contains 5 exons (109, 309, 159, 79 and 164 bp, respectively) and 4 introns (3436, 1125, 443 and 188 bp, respectively). The gene encoding C23 is located on Chromosome Xp 11.1 and is 1950 bp in length. The C23 gene contains 4 exons (169, 159, 79 and 181 bp, respectively) and 3 introns (429, 830, and 104 bp, respectively). Interestingly, exons 3 and 4 of C19 have a sequence identity with exons 2 and 3 of C23 greater than the overall sequence identity between the two complete proteins (i.e. greater than 48.8%) and exons 3 and 4 of C19 are identical in size to exons 2 and 3 of C23, respectively.
[0041] The expression of C19 and C23 is limited to the testes (see FIG. 1). To further characterize the expression of C19 and C23, antibodies were generated against C19 and C23. Those antibodies are specific for the target peptide and do not cross react with each other's repective lysozyme-like protein. C19 immunofluorescence and C19 and C23 EM localization experiments demonstrate that expression of the C19 and C23 proteins is localized in the sperm acrosome.
[0042] Recombinant C19 and C23 have been expressed in E. coli and in yeast. The proteins expressed in yeast were produced in a form that is secreted into the medium, and C19 was purified from the media and used in an assay to test for lysozyme activity. Secretion of the putatively processed forms of C19 and C23 (C23 was in crude form) as soluble proteins from Pichia pastoris revealed no lysozyme activity for C 19 and C23 using Micrococcus lysodeikticus as the lysozyme substrate. In particular, Micrococcus lysodeikticus was grown to confluence on a petri plate and the cells were contacted with 330 U of human lysozyme C (as a positive control), a reagent blank (as a negative control) and 1650 U of the purified soluble C19 protein (yrC19). Lysozyme activity was observed in the human lysozyme C portion (the positive control) as indicated by a zone of clearance about the introduce sample, but no activity was detected for yrC19. Although these compounds fail to exhibit lysozyme activity in the present assay, these compounds may still exhibit antibacterial/antiviral activity through an unknown mechanism.
[0043] Of all known lysozyme-C sequences (>75), 20 amino acid residues are invariant (see FIGS. 2 and 3). C19 contains all but two of those invariable amino acids (E35T, Y54N). The amino acid 35-E is considered a critical amino acid for catalytic function (i.e. cleaving the polysaccharide bond between N-actetylglucosamine and N-acetylmuramic acid). C23 contains all but one (D53E) of the 20 conserved amino acids. The amino acid 53-D is considered a critical ainino acid for catalytic function; however, g-type lysozymes do not have a D in the corresponding position. Homologous genes of C19 and C23 have also been isolated by applicants from other mammalian species (for example, mice), that contain similar mutations in the catalytic residues of these genes.
[0044] In accordance with one embodiment of the present invention, modified versions of the C19 and C23 proteins are provided wherein the 35-T of C19 is converted to 35-E (SEQ ID NO: 5) and the 53-E of C23 is converted to 53-D (SEQ ID NO: 6). It is anticipated that when these single amino acid substitutions are made in each lysozyme-like protein, the modified proteins will exhibit lysozyme activity and thus can be used as alternative compounds in all applications currently utilizing known human lysozyme-C. Furthermore, in one embodiment a modified version of C19 is prepared wherein the 35-T is converted to 35-E and 54-N is converted to 54-Y (SEQ ID NO: 7). This modified version of C19 is also expected to have lysozyme activity.
[0045] The C19 and C23 native polypeptides when modified to have lysozyme activity can be used in any of the applications described in U.S. Pat. No. 4,945,051, U.S. Pat. No. 5,585,257, U.S. Pat. No. 5,618,712 and WO 9924589 (DE19749973), the disclosures of which are expressly incorporated herein. The novel lysozymes of the present invention can also be used as the active agent in antibacterial wound dressings, dental plaque preventing formulations, anti-inflammatory throat lozenges, anti-acne compositions, sprays for controlling dry mouth condition and as food additives to prevent spoilage. It has also been reported that lysozyme may be effective against HI (Lee-Huang. S., PNAS 96:2678, 1999).
[0046] In one embodiment, a polypeptide comprising an amino acid sequence selected from the group consisting of SEQ ID NO: 8, SEQ ID NO: 9, SEQ ID NO: 10, and SEQ ID NO: II is used as the active agent in an antibacterial and antiviral composition. In one preferred embodiment, a polypeptidc comprising an amino acid sequence of SEQ ID NO: 10 or SEQ ID NO: 11 is used as an antibacterial and antiviral agent. The lysozyme proteins of the present invention can also be combined with standard antibacterial and antiviral agents to enhance the efficacy of those agents. In accordance with one embodiment, a composition comprising an amino acid sequence selected from the group consisting of SEQ ID NO: 8, SEQ ID NO: 9, SEQ ID NO: 10, and SEQ ID NO: 11 is used as an antibacterial/antiviral additives to intravaginal gels or foams to reduce the risk of sexually transmitted diseases.
[0047] In another embodiment, compositions comprising the native C19 or C23 polypeptides or fragments thereof are used as contraceptive agents. In particular, the unmodified C19 and C23 proteins are anticipated to have sperm specific functions that can be the basis of a contraceptive vaccine, designed to prevent capacitation/fertilization. For example in accordance with one embodiment the C19 or C23 polypeptides or fragments thereof, are used as components of a contraceptive vaccine.
[0048] In one aspect of the invention, C19 and C23 polypeptides (either separately or in combination) are delivered to a subject to elicit an active immune response. The vaccine acts as a temporary and reversible antagonist of the function of the egg surface proteins of the invention. For example, such vaccines could be used for active immunization of a subject, to raise an antibody response to temporarily block the sperm's access to the egg plasma antigen. In one aspect of the invention, an antigen could be administered at a certain period of the month, for example during ovulation of a female subject to block fertilization.
[0049] In another aspect of the invention, C19 and C23 polypeptides (either separately or in combination) are used as vaccines for permanent sterilization of a subject. Such vaccines can be used to elicit a T-cell mediated attack on the eggs, having an othoritic effect, useful as a method for irreversible sterilization. Methods for generating T-cell specific responses, such as adoptive immunotherapy, are well known in the art (see, for example, Vaccine Design, Michael F. Powell and Mark J. Newman Eds., Plenum Press, New York, 1995, pp 847-867). Such techniques may be particular useful for vetinary contraceptive or sterilization purposes, where a single dose vaccination may be desirable.
[0050] In one embodiment, the present invention is directed to a purified polypeptide comprising the amino acid sequence of SEQ ID NO: 2, or an amino acid sequence that differs from SEQ ID NO: 2 by one or more conservative amino acid substitutions. More preferably, the purified polypeptide comprises an amino acid sequence that differs from SEQ ID NO: 2 by 10 or less conservative amino acid substitutions. Alternatively, the polypeptide may comprise an amino acid sequence that differs from SEQ ID NO: 2 by 1 to 3 alterations, wherein the alterations are independently selected from a single amino acid deletion, insertion or substitution.
[0051] Alternatively, one embodiment of the present invention is directed to a purified polypeptide comprising the amino acid sequence of SEQ ID NO: 4, or an amino acid sequence that differs from SEQ ID NO: 4 by one or more conservative amino acid substitutions. More preferably, the purified polypeptide comprises an amino acid sequence that differs from SEQ ID NO: 4 by 10 or less conservative amino acid substitutions. Alternatively, the polypeptide may comprise an amino acid sequence that differs from SEQ ID NO: 4 by 1 to 3 alterations, wherein the alterations are independently selected from a single amino acid deletion, insertion or substitution.
[0052] Another embodiment of the present invention encompasses polypeptides comprising an amino acid sequence selected from the group consisting of SEQ ID NO: 5, SEQ ID NO: 6, SEQ ID NO: 7, SEQ ID NO: 8, SEQ ID NO: 9 and amino acid sequences that differs from SEQ ID NO: 5, SEQ ID NO: 6, SEQ ID NO: 7, SEQ ID NO: 8 or SEQ ID NO: 9 by 10 or less conservative amino acid substitutions. The present invention also encompasses fragments of SEQ ID NO: 2 and SEQ ID NO: 4, wherein the peptide fragment is at least ten amino acids in length and comprises ten contiguous amino acids that are identical in sequence to an ten contiguous amino portion of SEQ ID NO: 2 or SEQ ID NO: 4.
[0053] In one embodiment, the present invention provides methods of screening for agents, small molecules, or proteins that interact with polypeptides of SEQ ID NO: 2 or SEQ ID NO: 4. The invention encompasses both in vivo and in vitro assays to screen small molecules, compounds, recombinant proteins, peptides, nucleic acids, antibodies etc. which bind to or modulate the activity of C19 or C23 and are thus useful as therapeutics or diagnostic markers for fertility.
[0054] For example, the C19 or C23 polypeptide, or a bioactive fragment thereof, can be used to isolate ligands that bind to the respective native polypeptide under physiological conditions. The method comprises the steps of contacting the C19 or C23 polypeptide with a mixture of compounds under physiological conditions, removing unbound and non-specifically bound material, and isolating the compounds that remain bound to the C19 or C23 polypeptide. Typically, the C19 or C23 polypeptide will be bound to a solid support using standard techniques to allow rapid screening compounds. The solid support can be selected from any surface that has been used to immobilize biological compounds and includes but is not limited to polystyrene, agarose, silica or nitrocellulose. In one embodiment the solid surface comprises Fictionalized silica or agarose beads. Screening for such compounds can be accomplished using libraries of pharmaceutical agents and standard techniques known to the skilled practitioner.
[0055] In accordance with one embodiment the C19 and C28 polypeptides and peptide fragments are used to isolate oocyte proteins that bind to C19 and C28. The procedures for recovering oocyte proteins and screening for ligands that bind to C19 and C23 are well known to those skilled in the art. In one embodiment the C19 or C23 polypeptide is immobilized to a solid support and the proteins are contacted with a solution/suspension of oocyte proteins under conditions that allow binding. Unbound and non-specific bound materials are then washed from the solid support and the remaining bound materials are recovered and analyzed (by microsequencing, for example). Microsequencing of the recovered proteins will allow for the design of nucleic acid probes and primers for the identification and cloning of the corresponding genes that encode the recovered proteins.
[0056] The present invention also encompasses nucleic acid sequences that encode the C19 and C23 polypeptides, and bioactive fragments and derivatives thereof. In particular the present invention is directed to nucleic acid sequences Comprising the sequence of SEQ ID NO: 1, or SEQ ID NO: 3, or fragments thereof. In one embodiment, purified nucleic acids comprising at least 20 contiguous nucleotides (i.e, a hybridizable portion) that are identical to any 20 contiguous nucleotides of SEQ ID NO: 1 or SEQ ID NO: 3 are provided. In other embodiments, the nucleic acids comprises at least 25 (contiguous) nucleotides,-50 nucleotides, 100 nucleotides, or 200 nucleotides of SEQ ID NO: 1 or SEQ ID NO: 3.
[0057] One embodiment of the present invention includes nucleic acids that hybridize (under conditions defined herein) to all or a portion of the nucleotide sequence represented by SEQ ID NO: 1 or its complement. Alternatively, the present invention also includes nucleic acids that hybridize (under conditions defined herein) to all or a portion of the nucleotide sequence represented by SEQ ID NO: 3 or its complement. The hybridizing portion of the hybridizing nucleic acids is typically at least 15 (e.g., 20, 25, 30, or 50) nucleotides in length. Hybridizing nucleic acids of the type described herein can be used, for example, as a cloning probe, a primer (e.g., a PCR primer), or a diagnostic probe. The DNA sequence of SEQ ID NO: 1, SEQ ID NO: 3, or fragments thereof, can be used as probes to detect homologous genes from other vertebrate species.
[0058] Nucleic acid duplex or hybrid stability is expressed as the melting temperature or Tm, which is the temperature at which a nucleic acid duplex dissociates into its component single stranded DNAs. This melting temperature is used to define the required stringency conditions. Typically a 1% mismatch results in a 1° C. decrease in the Tm, and the temperature of the final wash in the hybridization reaction is reduced accordingly (for example, if two sequences having >95% identity, the final wash temperature is decreased from the Tm by 5° C.). In practice, the change in Tm can be between 0.5° C. and 1.5° C. per 1% mismatch.
[0059] The present invention is directed to the nucleic acid sequence of SEQ ID NO: 1 and SEQ ID NO: 3, and nucleic acid sequences that hybridize to those sequences (or fragments thereof) under stringent or highly stringent conditions. In accordance with the present invention highly stringent conditions are defined as conducting the hybridization and wash conditions at no lower than −5° C. Tm. Stringent conditions are defined as involve hybridizing at 68° C. in 5×SSC/5× Denhardt's solution/1.0% SDS, and washing in 0.2×SSC/0.1% SDS at 68° C. Moderately stringent conditions include hybridizing at 68° C. in 5×SSC/5× Denhardt's solution/1.0% SDS and washing in 3×SSC/0.1% SDS at 42° C. Additional guidance regarding such conditions is readily available in the art, for example, by Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, Cold Spring Harbor Press, N.Y.; and Ausubel et al. (eds.), 1995, Current Protocols in Molecular Biology, (John Wiley & Sons, N.Y.) at Unit 2.10.
[0060] In another embodiment of the present invention, nucleic acid sequences encoding the C19 or C23 polypeptides can be inserted into expression vectors and used to transfect cells to enhance the expression of those proteins on the target cells. In accordance with one embodiment, nucleic acid sequences encoding C19 or C23, or a fragment or a derivative thereof, are inserted into a eukaryotic expression vector in a manner that operably links the gene sequences to the appropriate regulatory sequences, and recombinant C19 or recombinant C23 is expressed in a eukaryotic host cell. Suitable eukaryotic host cells and vectors are known to those skilled in the art. In particular, nucleic acid sequences encoding C19 or C23 may be added to a cell or cells in vitro or in vivo using delivery mechanisms such as liposomes, viral based vectors, or microinjection. Accordingly, one aspect of the present invention is directed to transgenic cell lines that contain recombinant genes that express C19 or C23.
[0061] The present invention also encompasses antibodies, including anti-idiotypic antibodies, antagonists and agonists, as well as compounds or nucleotide constructs that inhibit expression of the C19 and C23 genes (transcription factor inhibitors, antisense and riboyme molecules, or gene or regulatory sequence replacement constructs), or promote expression of C19 and C23 (e.g., expression constructs in which C19 or C23 coding sequences are operatively associated with expression control elements such as promoters, promoter/enhancers, etc.). Antagonists of C19 and/or C23 function can be used to interfere with the-capacitation of vertebrate sperm and fertilization of an ovum, and thus used as contraceptive agents. Furthermore, antibodies against the C19 or C23 protein can be used for the diagnosis of conditions or diseases characterized by expression or overexpression of C19 or C23, or in assays to monitor patients being treated with C19 or C23 agonists, antagonists or inhibitors.
[0062] In accordance with one embodiment, antibodies are provided that specifically bind to C19 or C23. In particular, a C19 or C23 polypeptide, fragments thereof, or other derivatives, or analogs thereof, may be used as an immunogen to generate antibodies which immunospecifically bind such an imnmunogen. In accordance with one embodiment of the preset invention an antigenic compound is provided for generating antibodies, wherein the compound comprises an amino acid sequence selected from the group consisting of SEQ ID NO: 2, SEQ IDNO: 4, SEQ ID NO: 5, SEQ ID NO: 6, SEQ ID NO: 7, SEQ ID NO: 8 and SEQ ID NO: 9. The antibodies generated can be formulated with standard carriers and optionally labeled to prepare therapeutic or diagnostic compositions. Antibodies to C19 or C23 may be generated using methods that are well known in the art.
[0063] In one embodiment, rabbit polyclonal antibodies to an epitope of C19 or C23, is obtained. For the production of antibody, various host animals, including but not limited to rabbits, mice, rats, etc can be immunized by injection with a C19 or C23 peptide. Various adjuvants may be used to increase the immunological response, depending on the host species, and including but not limited to Freund's (complete and incomplete), mineral gels such as aluminum hydroxide, surface active substances such as lysolecithin, pluronic polyols, polyanions, peptides, oil emulsions, keyhole limpet hemocyanins, dimtrophenol, and potentially useful human adjuvants such as BCG (bacille Calmette-Guerin) and corynebacterium parvun.
[0064] For preparation of monoclonal antibodies directed toward an egg surface protein sequence or analog thereof, any technique which provides for the production of antibody molecules by continuous cell lines in culture may be used. For example, the hybridoma technique originally developed by Kohler and Milstein (1975, Nature 256:495-497), as well as the trioma technique, the human B-cell hybridoma technique (Kozbor et al., 1983, Immunology Today 4:72), and the EBV-hybridoma technique to produce human monoclonal antibodies (Cole et al., 1985, in Monoclonal Antibodies and Cancer Therapy, Alan R. Liss, Inc., pp. 77-96). In an additional embodiment of the invention, monoclonal antibodies can be produced in germ-free animals utilizing recent technology (PCT/US90/02545). According to the invention, human antibodies may be used and can be obtained by using human hybridomas (Cote et al., 1983, Proc. Natl. Acad. Sci. U.S.A. 80:2026-2030) or by transforming human B cells with EBV virus in vitro (Cole et al., 1985, in Monoclonal Antibodies and Cancer Therapy , Alan R. Liss, pp. 77-96). In fact, according to the invention, techniques developed for the production of “chimeric antibodies” (Morrison et al., 1984, Proc. Natl. Acad. Sci. U.S.A. 81:6851-6855; Neuberger et al., 1984, Nature 312:604-608; Takeda et al., 1985, Nature 314:452-454) by splicing the genes from a mouse antibody molecule specific for epitopes of C19 or C23 together with genes from a human antibody molecule of appropriate biological activity can be used; such antibodies are within the scope of this invention.
[0065] According to the invention, techniques described for the production of single chain antibodies (U.S. Pat. No. 4,946,778) can be adapted to produce egg surface protein-specific single chain antibodies. An additional embodiment of the invention utilizes the techniques described for the construction of Fab expression libraries (Fuse et al., 1989, Science 246:1275-1281) to allow rapid and easy identification of monoclonal Fab fragments with the desired specificity for egg surface proteins, derivatives, or analogs.
[0066] Antibody fragments which contain the idiotype of the molecule can be generated by known techniques. For example, such fragments include but are not limited to: the F(ab′) 2 fragment which can be produced by pepsin digestion of the antibody molecule; the Fab′ fragments which can be generated by reducing the disulfide bridges of the F(ab′) 2 fragment, the Fab fragments which can be generated by treating the antibody molecule with papain and a reducing agent, and Fv fragments.
[0067] In the production of antibodies, screening for the desired antibody can be accomplished by techniques known in the art, e.g ELISA (enzyme-linked immunosorbent assay). The foregoing antibodies can be used in methods known in the art relating to the localization and activity of the C19 or C23 proteins of the invention, e.g., for imaging these proteins, measuring levels thereof in appropriate physiological samples, in diagnostic methods, etc.
[0068] Antibodies generated in accordance with the present invention may include, but are not limited to, polyclonal, monoclonal, chimeric (i.e “humanized” antibodies), single chain (recombinant), Fab fragments, and fragments produced by a Fab expression library. These antibodies can be used as diagnostic agents for the diagnosis of conditions or diseases characterized by expression or overexpression of C19 or C23, or in assays to monitor patients being treated with C19 or C23 receptor agonists, antagonists or inhibitors. The antibodies useful for diagnostic purposes may be prepared in the same manner as those described above for therapeutics. The antibodies may be used with or without modification, and may be labeled by joining them, either covalently or non-covalently, with a reporter molecule.
[0069] In accordance with one embodiment an antibody is provided that specifically binds to a polypeptide selected from the group consisting of SEQ ID NO: 2, SEQ ID NO: 4, SEQ ID NO: 5, SEQ ID NO: 6, SEQ ID NO: 7, SEQ ID NO: 8 and SEQ ID NO: 9. In one preferred embodiment the antibody is a monoclonal antibody.
[0070] In one embodiment antibodies against the C19 and/or C23 proteins are used as contraceptive agents that prevent the binding of sperm cells to eggs. An experiment was conducted to determine if the antibodies against C19 and C23 could interfere human sperm's ability to bind to eggs (See Example 2). The assay was conducted in vitro using human sperm and hamster eggs. C19 and C23 are on the acrosome membrane and are only exposed upon permeablization of the acrosome. Only approximately ⅓ of sperm undergo acrosome reaction in vitro. As seen in Example 2, antibodies against C19 significantly interfered with sperm cells ability to bind to hamster eggs while no effect was observed for the antibody generated against C23. These results suggest that a unique receptor for the C19 protein may exist on mammalian eggs, and this receptor itself could serve as a target for contraceptive agents.
[0071] The present invention also encompasses compositions that can be placed in contact with sperm cells to inhibit the function of the C19 and C23 protein (i.e. either by inhibiting the expression of the C19 and C23 proteins or by interfering with the protein's function). In particular the compositions may comprise peptide fragments of C19 or C23, or analogs thereof that are taken up by the sperm cells and compete for binding with C19 and C23's natural ligands. Such inhibitory peptides can be modified to include fatty acid side chains to assist the peptides in penetrating the sperm cell membrane. Compositions comprising a C19 or C23 inhibitory agent can be used to modulate fertility of an individual, and in one embodiment, the inhibitory agents function as a male contraceptive pharmaceutical. In accordance with one embodiment a composition is provided that comprises an eight to fifteen amino acid sequence that is identical to an eight to fifteen contiguous amino acid sequence of SEQ ID NO: 2 or SEQ ID NO: 4 and a pharmaceutically acceptable carrier.
EXAMPLE 1
Isolation of the C19 and C23 Proteins
[0072] Materials and Methods
[0073] Solubilization and Electrophoresis of Human Spermatozoal Proteins
[0074] Preparation of semen specimens and solubilization of sperm proteins were performed as previously described (Naaby-Hanseii et al, 1997a.) For analytical two dimersional electrophoresis the detergent/urea extracted proteins were separated by isoelectric focusing (IEF) in acrylamide tube gels prior to second dimensional gel electrophoresis (SDS-PAGE), which was performed in a Protean II xi Multi-Cell apparatus (Bio-Rad, Richmond, Calif.) or on large format (23×23 cm) gels (Investigator 2-D Electrophoresis System, ESA) which were also employed for preparative 2D gel electrophoresis. Electrotransfer to nitrocellulose membranes and subsequent visualizing of the proteins by gold staining was accomplished as previously described (Naaby-Hansen et al, 1997) while electrotransfer to PVDF membranes (0.2 mm pore size, Pierce) was carried out as described by Henzel et al. (1993) using the transfer buffer composition of Matsudaira (1987) (10 mM 3-[cyclohexylamino]-1-propanesulfonic acid, 10% methanol, pH-11). The immobilized proteins were visualized by staining in a solution containing 0.1% Commassie R250, 40% methanol and 0.1% acetic acid for one minute, followed by destaining in a solution of 10% acetic acid and 50% methanol for 3×3 minutes.
[0075] Generation of Antiserum Against Gel Purified C19 and C23
[0076] The 86 kDa Coomassie-stained protein spot was cored from three 1.5 mrn thick 2-D SDS-PAGE gels of human sperm extracts. The gel cylinders were minced into a slurry in 1 ml of PBS and emulsified with an equal volume of complete Freunds adjuvant. Six hundred ul of this emulsion was intradermally injected into a New Zealand white rabbit, followed by two monthly subcutaneous booster injections of similarly-prepared antigen with incomplete Freunds adjuvant. Serum was collected 10 days after each booster injection.
[0077] Microsequencing of the C19 and C23 Proteins
[0078] The C19 and C23 stained protein spots were cored from a 1.5 mm thick 2D SDS-polyacrylamide gel and fragmented into smaller pieces. The proteins were destained in methanol, reduced in 10 mM ditlnothreitol and alkylated in 50 mM iodoacetamide in 0.1 M amnmonium bicarbonate. After removing the reagents, the gel pieces were incubated with 12.5 ng/ml trypsin in 50 MM ammonium bicarbonate overnight at 37° C. Peptides were extracted from the gel pieces in 50% acetonitrile in 5% formic acid and mierosequenced by tandem mass spectrometry and by Edman degradation at the Biomolecular Research Facility of the University of Virginia. Differentiation of leucine and isoleucine in the sequences were determined by Edman sequencing of HPLC isolated peptides. A degenerate deoxyinosine containing primers were used to isolate the C19 and C23 cDNA clones based on the microsequencing data and using PCR technology.
[0079] Northern and Dot Blot Analyses
[0080] A Northern blot containing 2 mg of poly(A) + RNA from eight selected human tissues was obtained from Clontech. The Northern blot was probed with a 32 P labeled C19 cDNA (FIG. 1A) or 32 P-labeled C23 cDNA (FIG. 1B). Probes were prepared by random oligonucleotide prime labeling (Feinberg and Vogelstein, 1983). Hybridization was performed in ExpressHyb solution (Clontech) at 68° C. for 1 h followed by three washes in 2×SSC, 0.05% SDS at room temperature and two washes in 0.1×SSC, 0.1% SDS for 20 min at 50° C.
[0081] A normalized RNA dot blot containing 89 to 514 ng of mRNA from 50 different human tissues was obtained from Clontech and probed with 32 P-labeled C19 EDNA or 32 P-labeled C23 cDNA. The normalized (100-500 ng) poly-(A)+ mRNAs present on the grid were isolated from various tissue sources including: whole brain, amygdala, caudate nucleus, cerebellum, cerebral cortex, frontal lobe, hippocampus, medulla oblongata, occipitallobe, putamen, substantia nigra, temporal lobe, thalamus, subthalnic nucleus, spinal chord, heart, aorta, skeletal muscle, colon, bladder, uterus, prostate, stomach, testis, ovary, pancreas, pituitary gland, adrenal gland, thyroid gland, salivary gland, mammary gland, kidney, liver, small intestine, spleen, thymus, peripheral leukocyte, lymph node, bone marrow, appendix, lung, trachea, placenta, fetal brain, fetal heart, fetal kidney, fetal liver, fetal spleen, fetal thymus, fetal lung, and 100 ng total yeast RNA, 100 ng yeast tRNA, 100 ng E. coli rRNA, 100 ng E. coli DNA, 100 ng poly r(A), 100 ng Cot 1 human DNA, 100 ng human DNA, 500 ng human DNA. The blot was hybridized in ExpressHyb solution (Clontech) containing salmon sperm DNA and human placental Cot-1 DNA overnight at 65° C. The blot was then washed three times in 2×SSC, 1% SDS at 65° C. followed by two additional washes in 0.1×SSC, 0.5% SDS at 55° C. before exposing the filter to X-Ray film. Hybridization was only detected in the testis RNA dot.
EXAMPLE 2
Human Sperm Binding and Fusion Assay Using Zona-Free Hamster Eggs
[0082] Sperm Preparation:
[0083] Motile sperm were harvested by the swim up method of Bronson and Fusi (1990). Briefly, a 500 ml sperm sample underlaid in 2 ml of BWW media containing 5 mg/mil HSA. Sperm were allowed to swim up for 1.5-2 h. Swimup sperm were collected and 8 ml of BWW+5 mg/ml HSA was added. The composition was spin at 600×g for 8 min at RT, the supernatant was removed and 8 ml of media was added to the pellet. The resuspended pellet was spun at 600×g for 8 min at RT. The supernatant was removed and 50 ml of EWW containing 30 mg/ml HSA was added to the pellet. Total sperm cells were counted and then incubated overnight in BWW+30 mg/ml HSA at a concentration of 20×10 6 sperm/i.
[0084] Egg Collection:
[0085] Female hamsters received i.p. injections of 30 IU PMSG followed by 30 IU of hCG 72 h later. 14-16 h following hCG injection, hamsters were sacrificed and oviducts are collected in BWW media containing 5 mg/ml HSA. Cumulus cells were removed with 1 mg/hnl hyaluronidase, the eggs were washed and zona pellucidae removed with 1 mg/ml trypsin. The eggs were then thoroughly washed and allowed to rest in the incubator.
[0086] Sperm/Antibody Incubation:
[0087] Sperm was diluted to 20×10 6 sperm/ml and incubated with appropriate dilutions of pre-immune or immune sera (initially a 1:10 and 1:50 dilution of sera is tested) in paraffin oil covered microdrops for 1 h.
[0088] Hamster eggs were added to the drops containing the sperm+antibody. The gametes were then co-incubated for 3 h.
[0089] Assessment of Binding and Fusion:
[0090] Eggs were washed free of unbound and loosely bound sperm by serial passage through 5 (50 ml) wash drops. The same pipet is used for all eggs washed in an individual experiment. Eggs are then stained by short-term (5-15 s) exposure to 1 mM acridine orange-3% DMSO in BSA/BWW (30 mg/nl), washed through 4 (50 ml) wash drops and mounted under 22×22 mm coverslips. Under UV illumination, unexpanded head s of oolemma-adherant sperm were counted and sperm that had penetrated the ooplasm exhibited expanded green heads. All experiments were repeated 3 times
Results 1:10 dilution of C19 Antibody Number of sperm bound per egg Pre Immune 38.2 Immune 21.8 P value = 7.78 × 10 6 Number of sperm fused per egg Pre Immune 3.2 Immune 2.9 P value = 0.6 1:10 dilution of C23 Antibody Number of sperm bound per egg Pre Immune 28.7 Immnune 27.4 P value = 0.79 Number of sperm fused per egg Pre Immune 1.8 Immune 1.6 P value = 0.71
[0091] [0091]
1
31
1
820
DNA
Homo sapiens
1
gccctggcaa ggttgtgggg gacatcttga gctgaagcag ggttttgagc cactgctgct 60
gctgccattg tcaccatggt ctcagctctg cggggagcac ccctgatcag ggtgcactca 120
agccctgttt cttctccttc tgtgagtgga ccacggaggc tggtgagctg cctgtcatcc 180
caaagctcag ctctgagcca gagtggtggt ggctccacct ctgccgccgg catagaagcc 240
aggagcaggg ctctcagaag gcggtggtgc ccagctggga tcatgttgtt ggccctggtc 300
tgtctgctca gctgcctgct accctccagt gaggccaagc tctacggtcg ttgtgaactg 360
gccagagtgc tacatgactt cgggctggac ggataccggg gatacagcct ggctgactgg 420
gtctgccttg cttatttcac aagcggtttc aacgcagctg ctttggacta cgaggctgat 480
gggagcaccg acaacgggat cttccagatc aacagccgga ggtggtgcag caacctcacc 540
ccgaacgtcc ccaacgtgtg ccggatgtac tgctcagatt tgttgaatcc taatctcaag 600
gataccgtta tctgtgccat gaagataacc caagagcctc agggtctggg ttactgggag 660
gcctggaggc atcactgcca gggaaaagac ctcactgaat gggtggatgg ctgtgacttc 720
taggatggac ggaaccatgc acagcaggct gggaaatgtg gtttggttcc tgacctaggc 780
ttgggaagac aagccagcga ataaaggatg gttgaacgtt 820
2
215
PRT
Homo sapiens
2
Met Val Ser Ala Leu Arg Gly Ala Pro Leu Ile Arg Val His Ser Ser
1 5 10 15
Pro Val Ser Ser Pro Ser Val Ser Gly Pro Arg Arg Leu Val Ser Cys
20 25 30
Leu Ser Ser Gln Ser Ser Ala Leu Ser Gln Ser Gly Gly Gly Ser Thr
35 40 45
Ser Ala Ala Gly Ile Glu Ala Arg Ser Arg Ala Leu Arg Arg Arg Trp
50 55 60
Cys Pro Ala Gly Ile Met Leu Leu Ala Leu Val Cys Leu Leu Ser Cys
65 70 75 80
Leu Leu Pro Ser Ser Glu Ala Lys Leu Tyr Gly Arg Cys Glu Leu Ala
85 90 95
Arg Val Leu His Asp Phe Gly Leu Asp Gly Tyr Arg Gly Tyr Ser Leu
100 105 110
Ala Asp Trp Val Cys Leu Ala Tyr Phe Thr Ser Gly Phe Asn Ala Ala
115 120 125
Ala Leu Asp Tyr Glu Ala Asp Gly Ser Thr Asp Asn Gly Ile Phe Gln
130 135 140
Ile Asn Ser Arg Arg Trp Cys Ser Asn Leu Thr Pro Asn Val Pro Asn
145 150 155 160
Val Cys Arg Met Tyr Cys Ser Asp Leu Leu Asn Pro Asn Leu Lys Asp
165 170 175
Thr Val Ile Cys Ala Met Lys Ile Thr Gln Glu Pro Gln Gly Leu Gly
180 185 190
Tyr Trp Glu Ala Trp Arg His His Cys Gln Gly Lys Asp Leu Thr Glu
195 200 205
Trp Val Asp Gly Cys Asp Phe
210 215
3
588
DNA
Homo sapiens
3
ctgggagggc ttacaggtgc cataatgaag gcctggggca ctgtggtagt gaccttggcc 60
acgctgatgg ttgtcactgt ggatgccaag atctatgaac gctgcgagct ggcggcaaga 120
ctggagagag cagggctgaa cggctacaag ggctacggcg ttggagactg gctgtgcatg 180
gctcattatg agagtggctt tgacaccgcc ttcgtggacc acaatcctga tggcagcagt 240
gaatatggca ttttccaact gaattctgcc tggtggtgtg acaatggcat tacacccacc 300
aagaacctct gccacatgga ttgtcatgac ctgctcaatc gccatattct ggatgacatc 360
aggtgtgcca agcagattgt gtcctcacag aatgggcttt ctgcctggac ttcttggagg 420
ctacactgtt ctggccatga tttatctgaa tggctcaagg ggtgtgatat gcatgtgaaa 480
attgatccaa aaattcatcc atgactcaga ttcgaagaga cagattttat cttcctttca 540
tttctttctc ttgtgcattt aataaaggat ggtatctata aacaatgc 588
4
159
PRT
Homo sapiens
4
Met Lys Ala Trp Gly Thr Val Val Val Thr Leu Ala Thr Leu Met Val
1 5 10 15
Val Thr Val Asp Ala Lys Ile Tyr Glu Arg Cys Glu Leu Ala Ala Arg
20 25 30
Leu Glu Arg Ala Gly Leu Asn Gly Tyr Lys Gly Tyr Gly Val Gly Asp
35 40 45
Trp Leu Cys Met Ala His Tyr Glu Ser Gly Phe Asp Thr Ala Phe Val
50 55 60
Asp His Asn Pro Asp Gly Ser Ser Glu Tyr Gly Ile Phe Gln Leu Asn
65 70 75 80
Ser Ala Trp Trp Cys Asp Asn Gly Ile Thr Pro Thr Lys Asn Leu Cys
85 90 95
His Met Asp Cys His Asp Leu Leu Asn Arg His Ile Leu Asp Asp Ile
100 105 110
Arg Cys Ala Lys Gln Ile Val Ser Ser Gln Asn Gly Leu Ser Ala Trp
115 120 125
Thr Ser Trp Arg Leu His Cys Ser Gly His Asp Leu Ser Glu Trp Leu
130 135 140
Lys Gly Cys Asp Met His Val Lys Ile Asp Pro Lys Ile His Pro
145 150 155
5
215
PRT
Homo sapiens
5
Met Val Ser Ala Leu Arg Gly Ala Pro Leu Ile Arg Val His Ser Ser
1 5 10 15
Pro Val Ser Ser Pro Ser Val Ser Gly Pro Arg Arg Leu Val Ser Cys
20 25 30
Leu Ser Ser Gln Ser Ser Ala Leu Ser Gln Ser Gly Gly Gly Ser Thr
35 40 45
Ser Ala Ala Gly Ile Glu Ala Arg Ser Arg Ala Leu Arg Arg Arg Trp
50 55 60
Cys Pro Ala Gly Ile Met Leu Leu Ala Leu Val Cys Leu Leu Ser Cys
65 70 75 80
Leu Leu Pro Ser Ser Glu Ala Lys Leu Tyr Gly Arg Cys Glu Leu Ala
85 90 95
Arg Val Leu His Asp Phe Gly Leu Asp Gly Tyr Arg Gly Tyr Ser Leu
100 105 110
Ala Asp Trp Val Cys Leu Ala Tyr Phe Glu Ser Gly Phe Asn Ala Ala
115 120 125
Ala Leu Asp Tyr Glu Ala Asp Gly Ser Thr Asp Asn Gly Ile Phe Gln
130 135 140
Ile Asn Ser Arg Arg Trp Cys Ser Asn Leu Thr Pro Asn Val Pro Asn
145 150 155 160
Val Cys Arg Met Tyr Cys Ser Asp Leu Leu Asn Pro Asn Leu Lys Asp
165 170 175
Thr Val Ile Cys Ala Met Lys Ile Thr Gln Glu Pro Gln Gly Leu Gly
180 185 190
Tyr Trp Glu Ala Trp Arg His His Cys Gln Gly Lys Asp Leu Thr Glu
195 200 205
Trp Val Asp Gly Cys Asp Phe
210 215
6
159
PRT
Homo sapiens
6
Met Lys Ala Trp Gly Thr Val Val Val Thr Leu Ala Thr Leu Met Val
1 5 10 15
Val Thr Val Asp Ala Lys Ile Tyr Glu Arg Cys Glu Leu Ala Ala Arg
20 25 30
Leu Glu Arg Ala Gly Leu Asn Gly Tyr Lys Gly Tyr Gly Val Gly Asp
35 40 45
Trp Leu Cys Met Ala His Tyr Glu Ser Gly Phe Asp Thr Ala Phe Val
50 55 60
Asp His Asn Pro Asp Gly Ser Ser Asp Tyr Gly Ile Phe Gln Leu Asn
65 70 75 80
Ser Ala Trp Trp Cys Asp Asn Gly Ile Thr Pro Thr Lys Asn Leu Cys
85 90 95
His Met Asp Cys His Asp Leu Leu Asn Arg His Ile Leu Asp Asp Ile
100 105 110
Arg Cys Ala Lys Gln Ile Val Ser Ser Gln Asn Gly Leu Ser Ala Trp
115 120 125
Thr Ser Trp Arg Leu His Cys Ser Gly His Asp Leu Ser Glu Trp Leu
130 135 140
Lys Gly Cys Asp Met His Val Lys Ile Asp Pro Lys Ile His Pro
145 150 155
7
215
PRT
Homo sapiens
7
Met Val Ser Ala Leu Arg Gly Ala Pro Leu Ile Arg Val His Ser Ser
1 5 10 15
Pro Val Ser Ser Pro Ser Val Ser Gly Pro Arg Arg Leu Val Ser Cys
20 25 30
Leu Ser Ser Gln Ser Ser Ala Leu Ser Gln Ser Gly Gly Gly Ser Thr
35 40 45
Ser Ala Ala Gly Ile Glu Ala Arg Ser Arg Ala Leu Arg Arg Arg Trp
50 55 60
Cys Pro Ala Gly Ile Met Leu Leu Ala Leu Val Cys Leu Leu Ser Cys
65 70 75 80
Leu Leu Pro Ser Ser Glu Ala Lys Leu Tyr Gly Arg Cys Glu Leu Ala
85 90 95
Arg Val Leu His Asp Phe Gly Leu Asp Gly Tyr Arg Gly Tyr Ser Leu
100 105 110
Ala Asp Trp Val Cys Leu Ala Tyr Phe Glu Ser Gly Phe Asn Ala Ala
115 120 125
Ala Leu Asp Tyr Glu Ala Asp Gly Ser Thr Asp Tyr Gly Ile Phe Gln
130 135 140
Ile Asn Ser Arg Arg Trp Cys Ser Asn Leu Thr Pro Asn Val Pro Asn
145 150 155 160
Val Cys Arg Met Tyr Cys Ser Asp Leu Leu Asn Pro Asn Leu Lys Asp
165 170 175
Thr Val Ile Cys Ala Met Lys Ile Thr Gln Glu Pro Gln Gly Leu Gly
180 185 190
Tyr Trp Glu Ala Trp Arg His His Cys Gln Gly Lys Asp Leu Thr Glu
195 200 205
Trp Val Asp Gly Cys Asp Phe
210 215
8
128
PRT
Homo sapiens
8
Lys Leu Tyr Gly Arg Cys Glu Leu Ala Arg Val Leu His Asp Phe Gly
1 5 10 15
Leu Asp Gly Tyr Arg Gly Tyr Ser Leu Ala Asp Trp Val Cys Leu Ala
20 25 30
Tyr Phe Thr Ser Gly Phe Asn Ala Ala Ala Leu Asp Tyr Glu Ala Asp
35 40 45
Gly Ser Thr Asp Asn Gly Ile Phe Gln Ile Asn Ser Arg Arg Trp Cys
50 55 60
Ser Asn Leu Thr Pro Asn Val Pro Asn Val Cys Arg Met Tyr Cys Ser
65 70 75 80
Asp Leu Leu Asn Pro Asn Leu Lys Asp Thr Val Ile Cys Ala Met Lys
85 90 95
Ile Thr Gln Glu Pro Gln Gly Leu Gly Tyr Trp Glu Ala Trp Arg His
100 105 110
His Cys Gln Gly Lys Asp Leu Thr Glu Trp Val Asp Gly Cys Asp Phe
115 120 125
9
138
PRT
Homo sapiens
9
Lys Ile Tyr Glu Arg Cys Glu Leu Ala Ala Arg Leu Glu Arg Ala Gly
1 5 10 15
Leu Asn Gly Tyr Lys Gly Tyr Gly Val Gly Asp Trp Leu Cys Met Ala
20 25 30
His Tyr Glu Ser Gly Phe Asp Thr Ala Phe Val Asp His Asn Pro Asp
35 40 45
Gly Ser Ser Glu Tyr Gly Ile Phe Gln Leu Asn Ser Ala Trp Trp Cys
50 55 60
Asp Asn Gly Ile Thr Pro Thr Lys Asn Leu Cys His Met Asp Cys His
65 70 75 80
Asp Leu Leu Asn Arg His Ile Leu Asp Asp Ile Arg Cys Ala Lys Gln
85 90 95
Ile Val Ser Ser Gln Asn Gly Leu Ser Ala Trp Thr Ser Trp Arg Leu
100 105 110
His Cys Ser Gly His Asp Leu Ser Glu Trp Leu Lys Gly Cys Asp Met
115 120 125
His Val Lys Ile Asp Pro Lys Ile His Pro
130 135
10
128
PRT
Homo sapiens
10
Lys Leu Tyr Gly Arg Cys Glu Leu Ala Arg Val Leu His Asp Phe Gly
1 5 10 15
Leu Asp Gly Tyr Arg Gly Tyr Ser Leu Ala Asp Trp Val Cys Leu Ala
20 25 30
Tyr Phe Glu Ser Gly Phe Asn Ala Ala Ala Leu Asp Tyr Glu Ala Asp
35 40 45
Gly Ser Thr Asp Tyr Gly Ile Phe Gln Ile Asn Ser Arg Arg Trp Cys
50 55 60
Ser Asn Leu Thr Pro Asn Val Pro Asn Val Cys Arg Met Tyr Cys Ser
65 70 75 80
Asp Leu Leu Asn Pro Asn Leu Lys Asp Thr Val Ile Cys Ala Met Lys
85 90 95
Ile Thr Gln Glu Pro Gln Gly Leu Gly Tyr Trp Glu Ala Trp Arg His
100 105 110
His Cys Gln Gly Lys Asp Leu Thr Glu Trp Val Asp Gly Cys Asp Phe
115 120 125
11
138
PRT
Homo sapiens
11
Lys Ile Tyr Glu Arg Cys Glu Leu Ala Ala Arg Leu Glu Arg Ala Gly
1 5 10 15
Leu Asn Gly Tyr Lys Gly Tyr Gly Val Gly Asp Trp Leu Cys Met Ala
20 25 30
His Tyr Glu Ser Gly Phe Asp Thr Ala Phe Val Asp His Asn Pro Asp
35 40 45
Gly Ser Ser Asp Tyr Gly Ile Phe Gln Leu Asn Ser Ala Trp Trp Cys
50 55 60
Asp Asn Gly Ile Thr Pro Thr Lys Asn Leu Cys His Met Asp Cys His
65 70 75 80
Asp Leu Leu Asn Arg His Ile Leu Asp Asp Ile Arg Cys Ala Lys Gln
85 90 95
Ile Val Ser Ser Gln Asn Gly Leu Ser Ala Trp Thr Ser Trp Arg Leu
100 105 110
His Cys Ser Gly His Asp Leu Ser Glu Trp Leu Lys Gly Cys Asp Met
115 120 125
His Val Lys Ile Asp Pro Lys Ile His Pro
130 135
12
126
PRT
Nasalis concolor
12
Lys Ile Phe Glu Arg Cys Glu Leu Ala Arg Thr Leu Lys Lys Leu Gly
1 5 10 15
Leu Asp Gly Tyr Lys Gly Val Ser Leu Ala Asn Trp Val Cys Leu Ala
20 25 30
Lys Trp Glu Ser Gly Tyr Asn Thr Glu Ala Thr Asn Tyr Asn Pro Asp
35 40 45
Glu Ser Thr Asp Tyr Gly Ile Phe Gln Ile Asn Ser Arg Tyr Trp Cys
50 55 60
Asn Asn Lys Thr Pro Gly Ala Val Asp Ala Cys His Ile Ser Cys Ser
65 70 75 80
Ala Leu Leu Gln Asn Asn Ile Ala Asp Ala Val Ala Cys Ala Lys Arg
85 90 95
Val Val Ser Asp Pro Gln Gly Val Arg Ala Trp Val Ala Trp Arg Asn
100 105 110
His Cys Gln Asn Lys Asp Val Ser Gln Tyr Val Lys Gly Cys
115 120 125
13
126
PRT
Nasalis concolor
13
Lys Ile Phe Glu Arg Cys Glu Leu Ala Arg Thr Leu Lys Lys Leu Gly
1 5 10 15
Leu Asp Gly Tyr Lys Gly Val Ser Leu Ala Asn Trp Val Cys Leu Ala
20 25 30
Lys Trp Glu Ser Gly Tyr Asn Thr Glu Ala Thr Asn Tyr Asn Pro Asp
35 40 45
Glu Ser Thr Asp Tyr Gly Ile Phe Gln Ile Asn Ser Arg Tyr Trp Cys
50 55 60
Asn Asn Lys Thr Pro Gly Ala Val Asp Ala Cys His Ile Ser Cys Ser
65 70 75 80
Ala Leu Leu Gln Asn Asn Ile Ala Asp Ala Val Ala Cys Ala Lys Arg
85 90 95
Val Val Ser Asp Pro Gln Gly Ile Arg Ala Trp Val Ala Trp Arg Asn
100 105 110
His Cys Gln Asn Lys Asp Val Ser Gln Tyr Val Lys Gly Cys
115 120 125
14
126
PRT
Macaca mulatta
14
Lys Ile Phe Glu Arg Cys Glu Leu Ala Arg Thr Leu Lys Lys Leu Gly
1 5 10 15
Leu Asp Gly Tyr Lys Gly Val Ser Leu Ala Asn Trp Val Cys Leu Ala
20 25 30
Lys Trp Glu Ser Gly Tyr Asn Thr Glu Ala Thr Asn Tyr Asn Pro Asp
35 40 45
Glu Ser Thr Asp Tyr Gly Ile Phe Gln Ile Asn Ser Arg Tyr Trp Cys
50 55 60
Asn Asn Lys Thr Pro Gly Ala Val Asp Ala Cys His Ile Ser Cys Ser
65 70 75 80
Ala Leu Leu Gln Asn Asn Ile Ala Asp Ala Val Ala Cys Ala Lys Arg
85 90 95
Val Val Ser Asp Pro Gln Gly Ile Arg Ala Trp Val Ala Trp Arg Asn
100 105 110
His Cys Gln Asn Arg Asp Val Ser Gln Tyr Val Lys Gly Cys
115 120 125
15
126
PRT
Macaca mulatta
15
Lys Ile Phe Glu Arg Cys Glu Leu Ala Arg Thr Leu Lys Arg Leu Gly
1 5 10 15
Leu Asp Gly Tyr Arg Gly Ile Ser Leu Ala Asn Trp Val Cys Leu Ala
20 25 30
Lys Trp Glu Ser Asp Tyr Asn Thr Gln Ala Thr Asn Tyr Asn Pro Asp
35 40 45
Gln Ser Thr Asp Tyr Gly Ile Phe Gln Ile Asn Ser His Tyr Trp Cys
50 55 60
Asn Asn Lys Thr Pro Gly Ala Val Asn Ala Cys Arg Ile Ser Cys Asn
65 70 75 80
Ala Leu Leu Gln Asp Asn Ile Ala Asp Ala Val Thr Cys Ala Lys Arg
85 90 95
Val Val Arg Asp Pro Gln Gly Ile Arg Ala Trp Val Ala Trp Arg Asn
100 105 110
His Cys Gln Asn Arg Asp Val Ser Gln Tyr Val Gln Gly Cys
115 120 125
16
126
PRT
Nasalis concolor
16
Lys Ile Phe Glu Arg Cys Glu Leu Ala Arg Thr Leu Lys Arg Leu Gly
1 5 10 15
Leu Asp Gly Tyr Arg Gly Ile Ser Leu Ala Asn Trp Val Cys Leu Ala
20 25 30
Lys Trp Glu Ser Gly Tyr Asn Thr Gln Ala Thr Asn Tyr Asn Pro Asp
35 40 45
Gln Ser Thr Asp Tyr Gly Ile Phe Gln Ile Asn Ser His Tyr Trp Cys
50 55 60
Asn Asn Lys Thr Pro Gly Ala Val Asn Ala Cys His Ile Ser Cys Asn
65 70 75 80
Ala Leu Leu Gln Asp Asn Ile Ala Asp Ala Val Thr Cys Ala Lys Arg
85 90 95
Val Val Arg Asp Pro Gln Gly Ile Arg Ala Trp Val Ala Trp Arg Asn
100 105 110
His Cys Gln Asn Arg Asp Val Ser Gln Tyr Val Gln Gly Cys
115 120 125
17
126
PRT
Gorilla gorilla
17
Lys Val Phe Glu Arg Cys Glu Leu Ala Arg Thr Leu Lys Arg Leu Gly
1 5 10 15
Met Asp Gly Tyr Arg Gly Ile Ser Leu Ala Asn Trp Met Cys Leu Ala
20 25 30
Lys Trp Glu Ser Gly Tyr Asn Thr Arg Ala Thr Asn Tyr Asn Ala Asp
35 40 45
Arg Ser Thr Asp Tyr Gly Ile Phe Gln Ile Asn Ser Arg Tyr Trp Cys
50 55 60
Asn Asp Lys Thr Pro Gly Ala Val Asn Ala Cys His Leu Ser Cys Ser
65 70 75 80
Ala Leu Leu Gln Asp Asn Ile Ala Asp Ala Val Ala Cys Ala Lys Arg
85 90 95
Val Val Arg Asp Pro Gln Gly Ile Arg Ala Trp Val Ala Trp Arg Asn
100 105 110
Arg Cys Gln Asn Arg Asp Val Arg Gln Tyr Val Gln Gly Cys
115 120 125
18
126
PRT
Homo sapiens
18
Lys Val Phe Glu Arg Cys Glu Leu Ala Arg Thr Leu Lys Arg Leu Gly
1 5 10 15
Met Asp Gly Tyr Arg Gly Ile Ser Leu Ala Asn Trp Met Cys Leu Ala
20 25 30
Lys Trp Glu Ser Gly Tyr Asn Thr Arg Ala Thr Asn Tyr Asn Ala Asp
35 40 45
Arg Ser Thr Asp Tyr Gly Ile Phe Gln Ile Asn Ser Arg Tyr Trp Cys
50 55 60
Asn Asp Lys Thr Pro Gly Ala Val Asn Ala Cys His Leu Ser Cys Ser
65 70 75 80
Ala Leu Leu Gln Asp Asn Ile Ala Asp Ala Val Ala Cys Ala Lys Arg
85 90 95
Val Val Arg Asp Pro Gln Gly Ile Arg Ala Trp Val Ala Trp Arg Asn
100 105 110
Arg Cys Gln Asn Arg Asp Val Arg Gln Tyr Val Gln Gly Cys
115 120 125
19
126
PRT
Leporinus elongatus
19
Lys Ile Tyr Glu Arg Cys Glu Leu Ala Arg Thr Leu Lys Lys Leu Gly
1 5 10 15
Leu Asp Gly Tyr Lys Gly Val Ser Leu Ala Asn Trp Met Cys Leu Ala
20 25 30
Lys Trp Glu Ser Ser Tyr Asn Thr Arg Ala Thr Asn Tyr Asn Pro Asp
35 40 45
Lys Ser Thr Asp Tyr Gly Ile Phe Gln Ile Asn Ser Arg Tyr Trp Cys
50 55 60
Asn Asp Lys Thr Pro Arg Ala Val Asn Ala Cys His Ile Pro Cys Ser
65 70 75 80
Ala Leu Leu Lys Asp Asp Ile Thr Gln Ala Val Ala Cys Ala Lys Arg
85 90 95
Val Val Ser Asp Pro Gln Gly Ile Arg Ala Trp Val Ala Trp Arg Asn
100 105 110
His Cys Gln Asn Gln Asp Leu Thr Pro Tyr Ile Arg Gly Cys
115 120 125
20
126
PRT
Colobus guereza
20
Lys Ile Phe Glu Arg Cys Glu Leu Ala Arg Thr Leu Lys Lys Leu Gly
1 5 10 15
Leu Asp Gly Tyr Lys Gly Val Ser Leu Ala Asn Trp Val Cys Leu Ala
20 25 30
Lys Trp Glu Ser Gly Tyr Asn Thr Asp Ala Thr Asn Tyr Asn Pro Asp
35 40 45
Glu Ser Thr Asp Tyr Gly Ile Phe Gln Ile Asn Ser Arg Tyr Trp Cys
50 55 60
Asn Asn Lys Thr Pro Gly Ala Val Asn Ala Cys His Ile Ser Cys Asn
65 70 75 80
Ala Leu Leu Gln Asn Asn Ile Ala Asp Ala Val Ala Cys Ala Lys Arg
85 90 95
Val Val Ser Asp Pro Gln Gly Ile Arg Ala Trp Val Ala Trp Lys Lys
100 105 110
His Cys Gln Asn Arg Asp Val Ser Gln Tyr Val Glu Gly Cys
115 120 125
21
126
PRT
Macaca mulatta
21
Lys Ile Phe Glu Arg Cys Glu Leu Ala Arg Thr Leu Lys Arg Leu Gly
1 5 10 15
Leu Asp Gly Tyr Arg Gly Ile Ser Leu Ala Asn Trp Val Cys Leu Ala
20 25 30
Lys Trp Glu Ser Asn Tyr Asn Thr Gln Ala Thr Asn Tyr Asn Pro Asp
35 40 45
Gln Ser Thr Asp Tyr Gly Ile Phe Gln Ile Asn Ser His Tyr Trp Cys
50 55 60
Asn Asn Lys Thr Pro Gly Ala Val Asn Ala Cys His Ile Ser Cys Asn
65 70 75 80
Ala Leu Leu Gln Asp Asn Ile Ala Asp Ala Val Thr Cys Ala Lys Arg
85 90 95
Val Val Ser Asp Pro Gln Gly Ile Arg Ala Trp Val Ala Trp Arg Asn
100 105 110
His Cys Gln Asn Arg Asp Val Ser Gln Tyr Val Gln Gly Cys
115 120 125
22
128
PRT
Aythya americana
22
Lys Val Tyr Ser Arg Cys Glu Leu Ala Ala Ala Met Lys Arg Leu Gly
1 5 10 15
Leu Asp Asn Tyr Arg Gly Tyr Ser Leu Gly Asn Trp Val Cys Ala Ala
20 25 30
Asn Tyr Glu Ser Gly Phe Asn Thr Gln Ala Thr Asn Arg Asn Thr Asp
35 40 45
Gly Ser Thr Asp Tyr Gly Ile Leu Gln Ile Asn Ser Arg Trp Trp Cys
50 55 60
Asp Asn Gly Lys Thr Pro Arg Lys Asn Ala Cys Gly Ile Pro Cys Ser
65 70 75 80
Val Leu Leu Arg Ser Asp Ile Thr Glu Ala Val Arg Cys Ala Lys Arg
85 90 95
Ile Val Ser Asp Gly Asp Gly Met Asn Ala Trp Val Ala Trp Arg Asn
100 105 110
Arg Cys Arg Gly Thr Asp Val Ser Lys Trp Ile Arg Gly Cys Arg Leu
115 120 125
23
128
PRT
Phasianus colchicus
23
Lys Val Tyr Gly Arg Cys Glu Leu Ala Ala Ala Met Lys Arg Leu Gly
1 5 10 15
Leu Asp Asn Tyr Arg Gly Tyr Ser Leu Gly Asn Trp Val Cys Ala Ala
20 25 30
Lys Tyr Glu Ser Asn Phe Asn Thr His Ala Thr Asn Arg Asn Thr Asp
35 40 45
Gly Ser Thr Asp Tyr Gly Ile Leu Gln Ile Asn Ser Arg Trp Trp Cys
50 55 60
Asn Asp Gly Lys Thr Pro Gly Arg Asn Leu Cys His Ile Pro Cys Ser
65 70 75 80
Ala Leu Leu Ser Ser Asp Ile Thr Ala Ser Val Asn Cys Ala Lys Lys
85 90 95
Ile Val Ser Asp Gly Asn Gly Met Asn Ala Trp Val Ala Trp Arg Asn
100 105 110
Arg Cys Lys Gly Thr Asp Val Ser Val Trp Thr Arg Gly Cys Arg Leu
115 120 125
24
128
PRT
Aythya americana
24
Lys Val Tyr Glu Arg Cys Glu Leu Ala Ala Ala Met Lys Arg Leu Gly
1 5 10 15
Leu Asp Asn Tyr Arg Gly Tyr Ser Leu Gly Asn Trp Val Cys Ala Ala
20 25 30
Asn Tyr Glu Ser Ser Phe Asn Thr Gln Ala Thr Asn Arg Asn Thr Asp
35 40 45
Gly Ser Thr Asp Tyr Gly Ile Leu Glu Ile Asn Ser Arg Trp Trp Cys
50 55 60
Asp Asn Gly Lys Thr Pro Arg Lys Asn Ala Cys Gly Ile Pro Cys Ser
65 70 75 80
Val Leu Leu Arg Ser Asp Ile Thr Glu Ala Val Lys Cys Ala Lys Arg
85 90 95
Ile Val Ser Asp Gly Asp Gly Met Asn Ala Trp Val Ala Trp Arg Asn
100 105 110
Arg Cys Lys Gly Thr Asp Val Ser Arg Trp Ile Arg Gly Cys Arg Leu
115 120 125
25
128
PRT
Phasianus colchicus
25
Lys Val Tyr Gly Arg Cys Glu Leu Ala Ala Ala Met Lys Arg Met Gly
1 5 10 15
Leu Asp Asn Tyr Arg Gly Tyr Ser Leu Gly Asn Trp Val Cys Ala Ala
20 25 30
Lys Phe Glu Ser Asn Phe Asn Thr Gly Ala Thr Asn Arg Asn Thr Asp
35 40 45
Gly Ser Thr Asp Tyr Gly Ile Leu Gln Ile Asn Ser Arg Trp Trp Cys
50 55 60
Asn Asp Gly Arg Thr Pro Gly Lys Asn Leu Cys His Ile Pro Cys Ser
65 70 75 80
Ala Leu Leu Ser Ser Asp Ile Thr Ala Ser Val Asn Cys Ala Lys Lys
85 90 95
Ile Val Ser Asp Gly Asn Gly Met Asn Ala Trp Val Ala Trp Arg Lys
100 105 110
His Cys Lys Gly Thr Asp Val Asn Val Trp Ile Arg Gly Cys Arg Leu
115 120 125
26
128
PRT
Ortalis vetula
26
Lys Ile Tyr Lys Arg Cys Glu Leu Ala Ala Ala Met Lys Arg Tyr Gly
1 5 10 15
Leu Asp Asn Tyr Arg Gly Tyr Ser Leu Gly Asn Trp Val Cys Ala Ala
20 25 30
Arg Tyr Glu Ser Asn Tyr Asn Thr Gln Ala Thr Asn Arg Asn Ser Asn
35 40 45
Gly Ser Thr Asp Tyr Gly Ile Leu Gln Ile Asn Ser Arg Trp Trp Cys
50 55 60
Asn Asp Gly Arg Thr Pro Gly Lys Asn Leu Cys His Ile Ser Cys Ser
65 70 75 80
Ala Leu Met Gly Ala Asp Ile Ala Pro Ser Val Arg Cys Ala Lys Arg
85 90 95
Ile Val Ser Asp Gly Asp Gly Met Asn Ala Trp Val Ala Trp Arg Lys
100 105 110
His Cys Lys Gly Thr Asp Val Ser Thr Trp Ile Lys Asp Cys Lys Leu
115 120 125
27
128
PRT
Phasianus colchicus
27
Lys Val Tyr Gly Arg Cys Glu Leu Ala Ala Ala Met Lys Arg Met Gly
1 5 10 15
Leu Asp Asn Tyr Arg Gly Tyr Ser Leu Gly Asn Trp Val Cys Ala Ala
20 25 30
Lys Phe Glu Ser Asn Phe Asn Thr Gly Ala Thr Asn Arg Asn Thr Asp
35 40 45
Gly Ser Thr Asp Tyr Gly Ile Leu Gln Ile Asn Ser Arg Trp Trp Cys
50 55 60
Asn Asp Gly Arg Thr Pro Gly Lys Asn Leu Cys His Ile Pro Cys Ser
65 70 75 80
Ala Leu Leu Ser Ser Asp Ile Thr Ala Ser Val Asn Cys Ala Lys Lys
85 90 95
Ile Val Ser Asp Gly Asp Gly Met Asn Ala Trp Val Ala Trp Arg Lys
100 105 110
His Cys Lys Gly Thr Asp Val Asn Val Trp Ile Arg Gly Cys Arg Leu
115 120 125
28
128
PRT
Phasianus colchicus
28
Lys Val Tyr Gly Arg Cys Glu Leu Ala Ala Ala Met Lys Arg Leu Gly
1 5 10 15
Leu Asp Asn Tyr Arg Gly Tyr Ser Leu Gly Asn Trp Val Cys Ala Ala
20 25 30
Lys Phe Glu Ser Asn Phe Asn Thr His Ala Thr Asn Arg Asn Thr Asp
35 40 45
Gly Ser Thr Asp Tyr Gly Ile Leu Gln Ile Asn Ser Arg Trp Trp Cys
50 55 60
Asn Asp Gly Arg Thr Pro Gly Arg Asn Leu Cys His Ile Pro Cys Ser
65 70 75 80
Ala Leu Leu Ser Ser Asp Ile Thr Ala Ser Val Asn Cys Ala Lys Lys
85 90 95
Ile Val Ser Asp Gly Asn Gly Met Asn Ala Trp Val Ala Trp Arg Asn
100 105 110
Arg Cys Lys Gly Thr Asp Val Asn Ala Trp Thr Arg Gly Cys Arg Leu
115 120 125
29
128
PRT
Phasianus colchicus
29
Lys Val Tyr Gly Arg Cys Glu Leu Ala Ala Ala Met Lys Arg Leu Gly
1 5 10 15
Leu Asp Asn Tyr Arg Gly Tyr Ser Leu Gly Asn Trp Val Cys Ala Ala
20 25 30
Lys Phe Glu Ser Asn Phe Asn Thr His Ala Thr Asn Arg Asn Thr Asp
35 40 45
Gly Ser Thr Asp Tyr Gly Ile Leu Gln Ile Asn Ser Arg Trp Trp Cys
50 55 60
Asn Asp Gly Arg Thr Pro Gly Arg Asn Leu Cys His Ile Ser Cys Ser
65 70 75 80
Ala Leu Leu Ser Ser Asp Ile Thr Ala Ser Val Asn Cys Ala Lys Lys
85 90 95
Ile Val Ser Asp Arg Asn Gly Met Asn Ala Trp Val Ala Trp Arg Asn
100 105 110
Arg Cys Lys Gly Thr Asp Val Asn Ala Trp Ile Arg Gly Cys Arg Leu
115 120 125
30
128
PRT
Macaca mulatta
30
Lys Ile Phe Glu Arg Cys Glu Leu Ala Arg Thr Leu Lys Lys Leu Gly
1 5 10 15
Leu Asp Gly Tyr Lys Gly Val Ser Leu Ala Asn Trp Val Cys Leu Ala
20 25 30
Lys Trp Glu Ser Gly Tyr Asn Thr Glu Ala Thr Asn Tyr Asn Pro Asp
35 40 45
Glu Ser Thr Asp Tyr Gly Ile Phe Gln Ile Asn Ser Arg Tyr Trp Cys
50 55 60
Asn Asn Gly Lys Thr Pro Gly Val Asp Ala Cys His Ile Ser Cys Ser
65 70 75 80
Ala Leu Leu Gln Asn Asn Ile Ala Asp Ala Val Ala Cys Ala Lys Arg
85 90 95
Val Val Ser Asp Pro Gln Gly Ile Arg Ala Trp Val Ala Trp Arg Asn
100 105 110
His Cys Gln Asn Arg Asp Val Ser Gln Tyr Val Lys Gly Cys Gly Val
115 120 125
31
128
PRT
Nasalis concolor
31
Lys Ile Phe Glu Arg Cys Glu Leu Ala Arg Thr Leu Lys Lys Leu Gly
1 5 10 15
Leu Asp Gly Tyr Lys Gly Val Ser Leu Ala Asn Trp Val Cys Leu Ala
20 25 30
Lys Trp Glu Ser Gly Tyr Asn Thr Glu Ala Thr Asn Tyr Asn Pro Asp
35 40 45
Glu Ser Thr Asp Tyr Gly Ile Phe Gln Ile Asn Ser Arg Tyr Trp Cys
50 55 60
Asn Asn Gly Lys Thr Pro Gly Val Asp Ala Cys His Ile Ser Cys Ser
65 70 75 80
Ala Leu Leu Gln Asn Asn Ile Ala Asp Ala Val Ala Cys Ala Lys Arg
85 90 95
Val Val Ser Asp Pro Gln Gly Ile Arg Ala Trp Val Ala Trp Arg Asn
100 105 110
His Cys Gln Asn Lys Asp Val Ser Gln Tyr Val Lys Gly Cys Gly Val
115 120 125 | The present invention relates to two novel, testis-specific proteins (C19 and C23) that arc lysozyme paralogues. The proteins are believed to play a role in capacitation of sperm and the fertilization of the ovum. Therefore these compounds make ideal targets for the design of contraceptive agents. The C19 and C23 proteins can also be modified to establish lysozyme activity and the modified proteins can then be used in all applications that currently exist for lysozymes. | 8 |
BACKGROUND OF THE INVENTION.
The invention relates to a heart pacemaker for generating a heart stimulation signal in the apparent absence of any heart stimulation signal during a given duration of time.
Generally, a demand heart pacemaker includes a detecting device for sensing and recognizing the occurrence of intracardiac voltage signals, and an interference recognition device for evaluating the intracardiac voltage signal senses to determine if it is an interference signal, and a signal generator operable to generate the heart stimulation signal a predetermined period of time after the sensing of a signal recognized as having the characteristics of heart stimulation signals.
Prior art demand heart pacemakers generally include an interference recognition device which distinguishes noise signals from heart stimulation signals by the fact that noise signals are repetitious. A typical prior art interference recognition device is described in the German Patent BD-AS 2,025,499 and includes a circuit comprising a capacitor arranged to have two discharge time constants, one by a discharge due a first resistor and the second one by discharge between a series arrangement of a diode and a second resistor. The first time constant is selected to be considerably greater than the second time constant.
The prior art interference recognition devices for heart pacemakers have presented many problems because they have difficulty in distinguishing many types of interference signals such as an interference signal lasting for a short time duration or one that is periodic or one that has an amplitude modulation within the physiological range. In addition, the prior art interference recognition devices cannot determine an interference signal at the early stages of the occurrence of the interference signal.
As a result of these deficiencies, the prior art heart pacemakers often erroneously identify an interference signal as being an acceptable intracardiac voltage signal and no heart stimulation signal is generated by the pacemaker. This loss of a heart stimulation signal creates a dangerous situation for the pacemaker patient.
Generally, interference signals of the type that can interfere with a heart pacemaker are commonplace everyday events. For example, the operation of push buttons for control devices can generate interference signals. Periodic closure of such push buttons can potentially interfere with the useful operation of prior art pacemakers. Interference signals can arise from electro-therapeutical equipment which can generate voltage signals similar in waveform to heart stimulation signals. In addition, inductively coupled interference voltages can occur in everyday life in a form of pulsed signals or amplitude modulated signals due to an electric arc welder or an electric melting furnace, particularly at the outset of operations.
The instant invention is an improved heart pacemaker due to the improved recognition of interference signals, particularly at their initial stages.
SUMMARY OF THE INVENTION
One of the principal objects of the invention is a heart pacemaker for generating a heart stimulation signal in the apparent absence of any heart signal during a given duration of time and includes interference detecting means operable for sensing intracardiac voltage signals possessing predetermined voltage waveform properties and operable for generating, respectively, first and second signals, the first signals being generated in response to the sensing of one of the intracardiac voltage signals by the detecting means and the second signals being generated whenever one of the intracardiac voltage signals is not succeeded by another voltage signal during a predetermined first period of time thus indicating that the first signals were not generated by interference signals, and generating means coupled to the detecting means and operable for generating the heart stimulation signal at the completion of a predetermined second period of time subsequent to the occurrence of one of the second signals and operable to have the second period of time interrupted in response to the occurrence of one of the second signals indicating that the first signals were produced by an action of the heart itself.
Further objects and advantages of the invention will be set forth in part in the following specification and in part will be obvious therefrom without being specifically referred to, the same being realized and attained as pointed out in the claims hereof.
The invention accordingly comprises the combination of elements and arrangements of parts which will be exemplified in a construction hereinafter set forth and the scope of the application of which will be indicated in the claims.
BRIEF DESCRIPTION OF THE DRAWINGS.
For a fuller understanding of the nature and objects of the invention, reference should be had to the following detailed description, taken in connection with the accompanying drawings, in which:
FIG. 1 shows curves illustrating the mode of operation of the instant invention;
FIG. 2 shows additional curves illustrating the mode of operation of the instant invention;
FIG. 3 shows a block diagram of one embodiment of the instant invention; and
FIG. 4 shows a block diagram of one embodiment of the interference detector device shown in the FIG. 3.
DESCRIPTION OF THE PREFERRED EMBODIMENT
To carry the invention into effect, one of the embodiments has been selected for illustration in the accompanying drawings and for description in this specification, reference being had to the FIGS. 1 to 4.
Generally, the instant invention makes use of the fact that an intracardiac voltage signal can be amplified and processed to derive a single voltage signal corresponding to the QRS complex. For example, it is known that the intracardiac unipolar EKG begins with a more or less distinctly formed positive spike or peak which is followed by a sharp negative slope and this is followed by oscillations possessing a low frequency and small amplitudes. The oscillations terminate after about 250 to 350 milliseconds.
Thus, if within a short monitoring period of time, only a single negative spike is detected, there is a high probability that the signal was produced by an action of the heart itself. The occurrence of multiple spikes within a short monitoring period of time would infer the presence of interference signals. This forms the basis for the instant invention.
Generally, experiments tend to suggest that for the instant invention the upper limit for the length of time for monitoring cardiac voltage signals is about 200 milliseconds. This approximate upper limit is based on experiments which show that a monitoring period of time greater than 200 milliseconds can cause complications in patients who have tachycardiac heart rhythm disturbances.
In addition, a longer monitoring period of time does not take into account the fact that practically no interference signal is likely to occur which does not possess at least several spikes or oscillations within a 200 milliseconds interval.
The lower limit for monitoring the cardiac voltage signals can be derived from the lowest frequency of the possible interference signals. For example, if alternating current at the common household frequency of 60 Hertz is a possible interference signal, then it can be easily calculated that the possible interference peaks can occur in an interval of about 16.6 milliseconds. From a practical point of view, a monitoring period of about 16.6 milliseconds is insufficient to detect interference signals with a high probability. Increasing the monitoring period to at least 1.5 times the period of the lowest expected interference signal substantially increases the likelihood of identifying an interference signal. For an expected interference signal having a frequency of 60 Hertz this gives a lower limit of 25 milliseconds for the monitoring.
If the possible interference signal has a frequency of 50 Hertz, similar calculations give a suggested lower limit for the monitoring period to be about 30 milliseconds. Similarly, if the interference signals could have a frequency of about 162/3 Hertz, then the lower limit for the suggested monitoring period should be about 90 milliseconds.
It has been determined that a monitoring time interval of from about 120 to about 150 milliseconds is preferred in order to detect with a high probability interference signals having very low frequencies.
FIG. 1 illustrates a case in which a spontaneous heart action occurs during a monitoring time period. The events in the FIG. 1 are as follows:
At time T o , a pulse signal I o is generated within the instant pacemaker and triggers the generation of a heart stimulation signal R o . The negative peak N o falls exceeds in absolute magnitude a predetermined threshold T S and is detected as being a possible heart stimulation signal. Thereafter, a monitoring interval Z U is commenced which corresponds to the first period of time and has a duration of about 120 milliseconds. No additional voltage signal having a negative peak below T S is detected during this period Z U . Thus, the instant circuit classifies the signal R o as being a heart stimulation signal and then commences a second period of time, the so-called demand period of time which lasts for a period of Z E . At time T 2 , a cardiac voltage signal R IEKG is detected as having a negative peak going below the threshold T S . This new signal interrupts the demand period Z E and initiates a new monitoring period Z U . During this new monitoring period, no additional trigger signal is sensed and this is taken to be an indication that the signal sensed at time T 2 was actually created by an EKG signal. At the end of this monitoring period Z U the second signal is generated at time T 3 to initiate the demand period Z E . Thus, the determination of whether a signal is a result of heart action is delayed by the time Z U .
During the time interval Z E as shown in the FIG. 1, no additional trigger signal is sensed and at time T 4 , a pulse signal I 4 is generated. The pulse signal I 4 initiates the generation of the stimulation pulse signal R 4 . The negative spike N 4 initiates the monitoring period Z U as shown.
The FIG. 2 shows the same operating sequence as FIG. 1 up to the time T 1 . At time T 5 , an interference signal R S having four oscillations is detected and these oscillations have a repetition period smaller than the time interval Z U . The negative-going half wave N 5 initiates the monitoring period Z U and the subsequent detection of the negative-going half wave N 6 inhibits the initiation of the demand period Z E . The negative-going half wave N 6 itself initiates a monitoring period Z U , but the occurrence of the negative-going half wave N 7 at time T 7 interrupts this period and initiates a new monitoring period Z U . At time T 8 , the occurrence of the negative-going half wave N 8 interrupts the monitoring period to start a new monitoring period. This monitoring period is concluded at time T 9 . At time T 10 , the demand interval Z E initiated at the time T 1 ends and a pulse signal I 10 is generated to produce the generation of a stimulation pulse at the stimulation electrode (not shown). The occurrence of this stimulation pulse signal initiates a new monitoring period Z U and the cycle of events continues.
FIG. 3 shows a preferred embodiment of the instant pacemaker. An intracardiac voltage signal IEKG is sensed by interference detecting means including amplifier 1, filter and trigger device 2, and interference detector 3. Generally, the amplifier 1 amplifies by about 500-fold. The filter and trigger device 2 includes a bandpass filter and generates a pulse signal which is coupled to the interference detector 3. The interference detector 3 determines if the sensed signal is a spontaneous heart signal or an interference signal.
Generating means including signal generator 4 which consists of a timing circuit responsible for the second period of time Z E and pulse generator 5 is coupled to the interference detector 3 and is responsive to signals generated by the interference detector 3. In the case of a sensed spontaneous heart signal, the signal generator 4 is inhibited for the demand period Z E . If, at the end of the demand period, no additional spontaneous heart signal is sensed, the pulse generator 5 generates a heart stimulation pulse signal which is coupled through lead 6 a stimulation electrode, to bring about an artificially induced contraction of the heart muscle. Generally, the same electrode is used for both sensing and intracardiac voltage signals and supplying a heart stimulation signal. A power supply 7 such as a battery is used to supply electrical power.
FIG. 4 is a block diagram of one embodiment of the interference detector 3. A retriggerable monostable multivibrator 10 is coupled to a NAND gate 11 and a monostable multivibrator 12. A counter 13 in the form of a "flip flop" is coupled to the NAND gate 11 and the multivibrator 12. An AND gate 14 is coupled to the multivibrator 12 and the counter 13.
The operation of the circuit is as follows:
Assume that a trigger signal S 1 (the above mentioned first signal) is generated by an incoming IEKG signal. This results in a logical high at the input terminal of the multivibrator 10. The multivibrator 10 remains in a stable state since it is triggered by the trailing edge. The output terminal of the NAND gate 11 retains a logical high, since the input terminal A is a logical low. Only when the signal S 1 changes from its logical high to its logical low will the multivibrator 10 change from its state of rest to its operating state, so that its output terminal Q will become a logical high. In correspondence, a logical high will appear at the input terminal A of the NAND gate 11. The input signal at the input terminal B, however, changes to its logical low, so that the output terminal of the NAND gate 11 remains at a logical high, due to the delay of the signals in the multivibrator 10.
Thus, the counter 13 does not change its state as a result of a non-repetitive signal. If no additional trigger signal is sensed during the monitoring period Z U , the duration of which is determined by the multivibrator 10, then the multivibrator 10 returns to its state of rest and sets the multivibrator 12 into action. The multivibrator 12 delays incoming signals so that the resetting of the counter 13 does not take place at the same time as the operation of the AND gate 14. Generally, the multivibrator 12 could include an RC unit.
When the counter 13 remains in a state of rest, its Q output terminal which is connected to the input terminal B of the AND gate 14 remains at a logical high. Any signal at the output terminal Q of the multivibrator 12 is coupled through the AND gate 14 (input terminal A) to the output terminal of the circuit forming the second signal S 2 which initiates the second period of time Z E .
When the monostable multivibrator 10 is in its operating position, the occurrence of a further trigger signal results in the following: the monostable multivibrator 10 is retriggerable so that a further trigger signal will extend its time interval by one monitoring period without allowing it to return to its state of rest. In addition, the further trigger signal changes the output terminal of the NAND gate 11 from a logical high to a logical low because a logical high is being applied to both input terminals A and B of the NAND gate 11. As a result of this, the counter 13 changes its state so that a logical low is applied to the input terminal B of the AND gate 14. If no further trigger signal occurs, then the monostable multivibrator 10 will return to its state of rest after a time period of one monitoring period Z U subsequent to the occurrence of the last trigger signal. This action sets the multivibrator 12 into action.
Due to the operating condition of the counter 13, the output terminal Q of the counter 13 is applied to the input terminal B of the AND gate 14 to produce a logical low, so that no signal is conducted any further by the multivibrator 12. When the monostable multivibrator 10 changes from its operating state to its state of rest, then the counter 13 is reset via the CLOCK input of the counter 13 by the trailing edge of the signal at the output terminal Q. The entire circuit is again in its original state.
Either the output terminal Q or the output terminal Q of the counter 13 can be used to indicate the presence of an interference signal. These output terminals can be used to adjust or increase the operating frequency of the pacemaker.
If more than two trigger signals occur within the monitoring period Z U , the mode of operation remains the same as in the case of two trigger signals not so occurring except that the monitoring period is extended by a time period of one monitoring period.
The circuit described herein can be used in connection with unipolar as well as bipolar stimulation electrodes. It is known, however, that unipolar stimulation electrodes are generally more susceptible to the coupling of interference signals than the bipolar electrodes. Thus, the instant invention is particularly advantageous for use in connection with unipolar stimulation electrodes.
We wish it to be understood that we do not desire to be limited to the exact details of construction shown and described, for obvious modifications will occur to a person skilled in the art. | A heart pacemaker for generating a heart stimulation signal in the apparent absence of any heart stimulation signal during a given duration of time, includes an interference detecting device for sensing intracardiac voltage signals which generate, respectively, first and second signals.
A retriggerable monostable first multivibrator is responsive to a trigger signal, so as to determine a first period of time, and, a second multivibrator is coupled to the first multivibrator, so as to operate for initiating a second period of time; the appearance of the second signals inhibits the heart stimulation signal; the first signal is generated in response to the sensing of one of the intracardiac voltage signals, and the second signals are generated whenever one of the intracardiac voltage signals is not succeeded by another voltage signal during the predetermined first period of time.
A generating device coupled to the detecting means may be operated for generating the heart stimulation signal at the completion of the occurrence of one of the second signals and may be operated to have the second period of time interrupted in response to the occurrence of a further one of the second signals. | 0 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation of U.S. application Ser. No. 08/542,730, filed on Oct. 13, 1995, now U.S. Pat. No. 5,696,801 which claims the benefit of U.S. Provisional application Ser. No. 60/003,266, filed on Aug. 24, 1995.
BACKGROUND OF THE INVENTION
The present invention relates generally to the field of suction strainers, and more particularly to the field of suction strainers employed in the suppression pools of boiling water reactor (BWR) nuclear power plants.
A suction strainer employed in a suppression pool removes solids from a flow of liquid (e.g., water) being drawn into an emergency core cooling system (ECCS) pump. The flow of water is drawn through the suction strainer and then into the suction line of the ECCS pump. Employment of suction strainers is desirable because solid debris drawn into the suction line of a pump can degrade pump performance by accumulating in the pump or its suction or discharge lines, or by impinging upon and damaging internal pump components.
While almost any pump degradation can be characterized as being costly, the degradation of ECCS pump performance at BWR nuclear plants can be detrimental to safe plant shutdown following a loss of coolant accident (LOCA). At a BWR nuclear power plant following a LOCA, it is critical for the ECCS pumps to operate for an extended period of time in an undegraded fashion. In one mode of operation, the ECCS pumps are operated to recirculate water from the suppression pool back to the reactor core for the purpose of core cooling. A LOCA results from a high pressure pipe rupturing with such great force that large quantities of debris, such as pipe and vessel insulating material, and other solids, may be washed into the suppression pool. Conventional ECCS suction strainers currently installed in BWR plants would have a tendency to become clogged by such debris due to their small size and poor design. Also, when the large pressure pipes rupture with great force, suction strainers in the suppression pool are subjected to great hydrodynamic forces that can damage the suction strainers as well as subject the attachment recirculation piping to large reactive forces. These structural considerations, and space constraints, limit the size and shape of suction strainers in suppression pools.
Conventional BWR plant suction strainers are typically constructed and arranged in a manner such that, under full flow conditions, localized high entrance velocities are established through that portion of the suction strainer that is most proximate to the suction line of the pump, while low entrance velocities are established through that portion of the suction strainer that is more distant from the suction line of the pump. The high entrance velocities may draw more solid debris into contact with the suction strainer causing the portions of the suction strainer experiencing the high entrance velocities to experience higher head loss. As the portion of the suction strainer most proximate to the suction line collects debris, high entrance velocities are established at the portion of the suction strainer that is next closest to the suction line causing that portion to collect debris. This process often continues until the entire suction strainer has collected debris in varying quantities, resulting in a non-uniform build-up of debris on the outer surface of the strainer.
Localized high entrance velocities can be detrimental even when solids are not present in the liquid being pumped. For example, high entrance velocities can result in turbulent flow which tends to create greater pressure losses than laminar flow. Any such pressure losses reduce the net positive suction head (NPSH) available to a pump. As the NPSH available decreases, pump cavitation may occur. Similarly, localized high entrance velocities can cause vortexing. When a suction strainer is not sufficiently submerged, the vortexing can cause air ingestion which can severely degrade pump performance.
Attempts have been made to resolve certain of the problems associated with suction strainer-like devices in other applications. For example, cylindrical suction flow control pipes have been encircled with screen material and employed in water wells. Such wells typically employ a well pump above the ground surface and a riser pipe extending from the well pump to the water table. The suction flow control pipe is connected to the end of the riser pipe and extends further below the water table. Openings are defined through the side wall of the suction flow control pipe such that there is somewhat less open area near the riser pipe and somewhat more open area distant from the riser pipe. As a result, when water is drawn into the flow control pipe through the openings, a substantially uniform inflow distribution is defined along the length of the flow control pipe. While such suction flow control pipes offer some advantages, they are not suitable for all applications.
Attempts have been made, totally separate from flow control pipes, to increase filtering surface areas of BWR ECCS suction strainers in an effort to decrease pressure losses and thereby prevent pump cavitation. For example, such suction strainers may include a plurality of spaced, coaxial, stacked filtering disks. More particularly, such stacked disk suction strainers typically include an annular flange for attachment to the corresponding flange on the pump suction line. The stacked disk suction strainer provides an enhanced surface area and defines a longitudinal axis that is encircled by the attachment flange. A first disk is attached to the attachment flange. The first disk includes a pair of a radially extending, circular, disk walls, each of which encircle the longitudinal axis, and define a central hole. A first disk wall of the pair of disk walls is connected to the attachment flange. The first and second disk wall of the pair of disk walls face one another and are separated by a slight longitudinal distance. The first disk further includes an outer annular wall that encircles the longitudinal axis. The outer annular wall includes an annular first edge and an annular second edge. The entirety of the annular first edge of the outer annular wall is connected to the entire peripheral edge of the first perforated disk wall; and the entirety of the annular second edge of the outer annular wall is connected to the entire peripheral edge of the second perforated disk wall such that the pair of disk walls are connected at their periphery.
The stacked disk suction strainer further includes a plurality of inner annular walls that encircle the longitudinal axis, each of which includes an annular first edge and an annular second edge. The annular first edge of one of the inner annular walls is connected around the periphery of the central hole of the second disk wall. The annular second edge of that inner annular wall is connected around the periphery of the central hole of a disk wall of a second disk. The first and second disk walls, and the outer and inner annular walls are perforated and comprise the filtering surface of the stacked disk suction strainer. Additional perforated disks and inner annular walls are attached to one another in the above manner until the last disk is attached, wherein the outer disk wall of the last disk does not include a central hole. The stacked disk suction strainers may incorporate separate structural members to maintain the structural integrity of the stacked disk suction strainer. However, the conventional stacked disk suction strainers do not incorporate an internal core tube and related components, whereby the conventional stacked disk suction strainers are difficult to structurally reinforce and are susceptible to vortexing and the detrimental non-uniform localized entrance velocities discussed above.
There is, therefore, a need in the industry for an improved suction strainer.
SUMMARY OF THE INVENTION
Briefly described, the preferred embodiments of the present invention include a suction strainer that includes a filtering device with a strategically enlarged filtering surface and an internal core. The internal core is preferably in the form of an internal core tube, which is preferably an internal pipe with flow openings. In accordance with the preferred embodiments of the present invention, the internal core tube structurally reinforces the filtering device.
In accordance with the preferred embodiments of the present invention, the structural reinforcement provided by the internal core tube is enhanced by reinforcing structural members that extend radially from the internal core tube. The reinforcing structural members are preferably connected to and extend radially from and angularly around the internal core tube to structurally support the filtering surfaces of the external filtering structure. The internal core tube, in conjunction with the structural members, seeks to prevent air ingestion and vortexing. The suction strainer preferably extends away from the suction line of an ECCS pump to define a length, and in accordance with certain examples the preferred embodiments of the present invention, the internal core tube seeks to promote controlled inflow along the length to preclude the establishment of non-uniform localized entrance velocities through the filtering surface. In accordance with other examples of the preferred embodiments of the present invention, the internal core tube is not constructed to specifically promote such a uniform inflow along the length.
In accordance with the preferred embodiments of the present invention, the suction strainer is constructed in a manner that seeks to enlarge the filtering surface while minimizing the projected area of the suction strainer. The minimization of the projected area as well as structural reinforcement of the suction strainer enables the suction strainer to withstand high levels of hydrodynamic impact loading following a LOCA. The suction strainer also serves to minimize the bending moment and other reactive forces on the attachment ECCS piping in the BWR suppression pool.
In accordance with the preferred embodiments of the present invention, the filtering surface is defined by an external filtering structure that is attached to, extends from, and is built around the internal core tube and the reinforcing structural members. When the suction strainer is connected to the suction line of a pump and submerged, a liquid flow path is established through the internal core tube and external filtering structure. The liquid originates exterior to the external filtering structure and is drawn through the filtering surfaces of the external filtering structure. The filtering surfaces separate solids from the liquid. The size of the filtering surface is enlarged by virtue of the fact that the filtering surface defines protrusions such that the distance that the filtering surface extends from the internal core tube alternates. The resulting enlarged filtering surface seeks to decrease average flow velocities through the filtering surface and thereby spread the collected solid debris in thinner layers, thereby decreasing overall pressure losses associated with the suction strainer. Once the liquid flows through the filtering surface, the liquid is drawn through the internal core tube and into the suction line of the pump.
In accordance with the preferred embodiments of the present invention, the protrusions of the external filtering structure are in the form of a plurality of filtering plate assemblies that are connected to and extend radially from the internal core tube. Each plate assembly includes a pair of plate walls that face one another, define a distance therebetween, and are connected at their peripheries by an outer wall that surrounds the internal core tube. A separation distance is defined between neighboring plate assemblies. Inner walls connect between neighboring plate assemblies and extend around the internal core tube at a radius less than the radius of the outer walls. The outer and inner walls as well as the plate walls are perforated and comprise the filtering surfaces of the suction strainer. In accordance with first and second preferred embodiments of the present invention, the plurality of plate assemblies are preferably in the form of stacked disks that are spaced to defined troughs therebetween. In accordance with other embodiments, the plate assemblies are in other forms that increase the surface area of the suction strainer.
In accordance with preferred embodiments of the present invention, the internal core tube has a downstream end for connection to the pump suction flange and an upstream end distant from the downstream end. The internal core tube defines a longitudinal axis extending between the upstream and downstream ends. In accordance with the preferred embodiments of the present invention, a plurality of openings are defined through the side wall of the internal core tube. In accordance with certain examples of the preferred embodiments, the openings are constructed and arranged such that there is somewhat less open area near the downstream end than the upstream end, and the amount of open area tapers between the upstream end and the downstream end. As a result, when water flows into the internal core tube through the openings, a substantially uniform flow rate distribution is defined along substantially the entire length of the internal core tube.
It is therefore an object of the present invention to provide an improved BWR ECCS suction strainer.
Another object of the present invention is to increase safety by improving the operability of the ECCS of a BWR nuclear plant following a LOCA.
Yet another object of the present invention is to structurally reinforce a suction strainer sufficiently so that it can withstand the hydrodynamic forces following a LOCA in the suppression pool at a BWR nuclear plant.
Still another object of the present invention is to minimize reactive forces on the attachment ECCS piping following a LOCA.
Still another object of the present invention is to maximize the total strainer surface area within a limited geometric profile while providing a maximum strength strainer.
Still another object of the present invention is to simultaneously minimize both the thickness of collected debris on the strainer and the average entrance velocities to minimize the resultant NPSH of the ECCS following a LOCA.
Still another object of the present invention is to maximize the amount of time required to reach a particular head loss across the strainer.
Still another object of the present invention is to control the distribution of fluid flow over the strainer so as to collect debris uniformly, from disk to disk or from trough to trough, to allow scaling of the strainer for other flow rates with similar, but different size, strainers with different water flow rates.
Still another object of the present invention is to prevent vortexing and air ingestion.
Other objects, features and advantages of the present invention will become apparent upon reading and understanding this specification, taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic, downstream end, perspective view of a suction strainer with an internal core tube in accordance with one example of the first preferred embodiment of the present invention.
FIG. 2 is a schematic, partially cut-away, upstream end, perspective view of the suction strainer of FIG. 1.
FIG. 3 is a schematic, side elevational view of a suction strainer with an internal core tube in accordance with one example of the second preferred embodiment of the present invention.
FIG. 4 is a schematic, upstream end, elevational view of the suction strainer of FIG. 3.
FIG. 5 is an isolated, plan view an internal core tube of the suction strainer of FIG. 3, wherein the internal core tube is in an unrolled and flattened configuration.
FIG. 6 is an isolated, schematic, elevational view of a wall of a filtering portion of the suction strainer of FIG. 3.
FIG. 7 is an isolated, plan view of a structural member of the filtering portion of the suction strainer of FIG. 3.
FIG. 8 is an isolated, schematic, plan view an outer wall of the filtering portion of the suction strainer of FIG. 3, wherein the outer wall is in an unrolled and flattened configuration.
FIG. 9 is an isolated, schematic, plan view an inner wall of the filtering portion of the suction strainer of FIG. 3, wherein the inner wall is in an unrolled and flattened configuration.
FIG. 10 is a schematic representation of portions of a BWR nuclear power plant, wherein the suction strainer of FIG. 1 is connected the ECCS of the power plant.
FIG. 11 is a schematic, side elevational view of a suction strainer with an internal core tube in accordance with an alternate embodiment of the present invention.
FIG. 12 is a schematic, upstream end, elevational view of a suction strainer with an internal core tube in accordance with another alternate embodiment of the present invention.
FIG. 13 is a schematic, side elevational view of the suction strainer of FIG. 12.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now in greater detail to the drawings, in which like numerals represent like components throughout the several views, FIG. 1 is a schematic, perspective view of a suction strainer 20 with a core, in accordance with the first example of the first preferred embodiment of the present invention. The core is in the form of an internal core tube 26, and the suction strainer 20 further includes an upstream end 22, an opposite downstream end 24, and an exterior filtering structure 28 connected to and at least partially bounding the internal core tube 26. In accordance with the first preferred embodiment of the present invention, the internal core tube 26 is preferably in the form of a cylinder that structurally reinforces exterior filtering structure 28. The internal core tube 26 extends between the ends 22,24 and protrudes from the filtering structure 28 at the downstream end 24. The internal core tube 26 includes a core wall 30 that encircles and defines a core chamber 32. The core wall further defines a primary opening 33 that provides access to the core chamber 32, and the longitudinal axis 34 of the suction strainer 20. The portion of the core wall 30 that is internal to the filtering structure 28 preferably defines a plurality of openings therethrough (for example, see openings 74,76,78 defined through core wall 30' in FIG. 5), as will be discussed in greater detail below. The portion of the core wall 30 that extends from the filtering structure 28 at the downstream end 24 is preferably not perforated.
The filtering structure 28 encircles a majority of the internal core tube 26 and includes an exterior filtering surface 40. FIG. 1 is schematic in nature because, as will be discussed in greater detail below, the entire filtering surface 40 is preferably perforated (i.e., the filtering surface 40 defines a plurality of openings therethrough). The perforations are not depicted in FIG. 1 in an effort to clarify the view. The filtering surface 40 further defines a plurality of protrusions such that the contour of the filtering surface 40 is varied to uniquely maximize the effective filtering area of the filtering surface 40 within a limited geometric profile described by the length and outer diameter of the suction strainer 20. The filtering structure 28 includes a plurality of spaced protrusions which cooperate to define peaks and valleys. In accordance with the first preferred embodiment of the present invention, the protrusions are in the form of plate assemblies 42a-c which are preferably in the form of circular disks, and the valleys defined between the disks are in the form of annular troughs. In accordance with the first preferred embodiment of the present invention, the disk and troughs are preferably arranged in a uniform and consistent pattern. While the suction strainer 20 is constructed in a manner that seeks to maximize its filtering surfaces 40, that construction also seeks to reduce the projected area of the suction strainer 20 such that the suction strainer 20 can withstand both high levels of hydrodynamic impact loading and minimize bending moments on the attachment piping 102 (FIG. 10).
An annular connection flange 38 encircles and is connected to the core wall 30 at the downstream end 24. The connection flange 38 is preferably constructed and arranged for attachment to a corresponding flange (not shown) in the suction line 102 (FIG. 10) of a pump 104 (FIG. 10). The connection flange 38 is depicted in simplified form in FIG. 1 in an effort to clarify the view. The connection flange 38 preferably includes a plurality of bolt holes (not shown) therethrough that facilitate connection to the corresponding flange, as should be understood by those reasonably skilled in the art. In accordance with the preferred embodiments of the present invention, the connecting flange 38 refers, for example and not limitation, to a standard bolted flange connection. In accordance with alternate embodiments of the present invention a flange 38 is not employed, and the suction strainer 20 is connected to the suction line 102 by virtue of threading, welding, or other conventional fastening techniques or devices.
When the suction strainer 20 is connected to the suction line 102 (FIG. 10) of an ECCS pump 104 (FIG. 10), liquid is drawn into the suction strainer 20 through the perforations defined through the filtering surface 40. The filtering surface 40 functions to collect solids (not shown) on the suction strainer 20. Once liquid is drawn through the filtering surface 40, the liquid is drawn through the openings (for example, see openings 74,76,78 in FIG. 5) defined through that portion of the core wall 30 that is internal to the filtering structure 28.
Referring back to the plate assemblies 42a-c, they preferably encircle the longitudinal axis 34, and the exposed surfaces of the plate assemblies 42a-c constitute a substantial portion of the filtering surface 40. The plate assemblies 42a-c include perforated plate walls 44a-f and perforated outer annular walls 46a-c that preferably encircle the longitudinal axis 34. More particularly, and representative of the construction of the plate assemblies 42b,c, the plate assembly 42a includes the plates walls 44a,b which face one another and are separated by a longitudinal distance. The plate walls 44a,b each define a peripheral edge (as an example, see peripheral edge 47 of plate wall 44' in FIG. 6), and the outer wall 46a spans and is connected between the peripheral edge of the plate wall 44a and the peripheral edge of the plate wall 44b. Each of the plate walls 44a-e define a plate hole (as an example, see plate hole 48 of plate wall 44' in FIG. 6) therethrough, and the plate holes are preferably circular and centered with respect to their respective plate wall 44a-e. The internal core tube 26 extends and is connected through the plate holes (as an example, see plate hole 48 of plate wall 44' in FIG. 6). The filtering structure 28 further includes a plurality of inner walls 43a,b. The inner walls 43a,b are preferably annular. The inner walls 43a,b are also preferably perforated such that they constitute the remainder of the filtering surface 40. The inner walls 43a,b preferably encircle the longitudinal axis 34, and the inner wall 43a is connected between the plate assemblies 42a,b while the inner wall 43b is connected between the plate assemblies 42b,c.
FIG. 2 is a schematic, partially cut-away, upstream end, perspective view of the suction strainer 20, in accordance with the first example of the first preferred embodiment of the present invention. Portions of the plate assemblies 42b,c and the inner wall 43b are cut-away to expose the portion of the internal core tube 26 that is proximate to the upstream end 22. FIG. 2 is schematic in nature by virtue of the fact that perforations are not shown extending through the plate assemblies 42a-c or the inner walls 43a,b, and the openings (for example, see openings 74,76,78 in FIG. 5) that extend through the core wall 30 are not depicted in an effort to clarify the view. As mentioned above, the plate walls 44a-e each define a plate hole (for example see plate hole 48 in FIG. 6) therethrough, through which the internal core tube 26 extends and is connected. Conversely, the plate wall 44f, which is partially cut-away in FIG. 2, does not define such a plate hole such that the plate wall 44f functions to cover the upstream end 22 of the internal core tube 26 and the core chamber 32. Except for that difference between the plate wall 44f and the other plate walls 44a-e, the plate assembly 42c is representative of the plate assemblies 42a,b.
In accordance with the first preferred embodiment of the present invention, the internal core tube 26 functions as a structural member that supports the filtering structure 28. The filtering structure 28 and the internal core tube 26 are interconnected in a manner that synergistically strengthens the suction strainer 20. In accordance with the first preferred embodiment of the present invention, the strengthening is enhanced by a plurality of structural members 50 that are preferably rectangular and planar. The structural members 50 are disposed within and are effectively part of each of the plate assemblies 42a-c. Some of the structural members 50 are cut-away in FIG. 2 to clarify the view. In accordance with the first preferred embodiment of the present invention, the strengthening is also enhanced by a plurality of shorter structural members 52 that are preferably rectangular and planar. Structural members 52 are associated with each of the inner walls 43a,b. In accordance with the first preferred embodiment of the present invention, the structural members 50,52 are solid. In accordance with alternate embodiments of the present invention, holes or other perforations are defined through the structural members 50,52. In accordance with the first preferred embodiment of the present invention, the solid structural members 50,52 function to both structurally reinforce the filtering structure 28 and prevent vortexing and air ingestion.
More particularly, and representative of the construction of the plate assemblies 42a,b, the structural members of plate assembly 42c extend radially from the core wall 30 and are angularly displaced about the longitudinal axis 34. Each of the structural members 50 includes an inner edge (for example, see inner edge 54 of structural member 50' in FIG. 7) connected to the core wall 30, an opposite outer edge (for example, see outer edge 56 in FIG. 7) connected to the outer annular wall 46c, a side edge (for example, see side edge 58 in FIG. 7) connected to the plate wall 44f, and an opposite side edge (for example, see side edge in FIG. 7) connected to the plate wall 44e. Further, and representative of the plate assemblies 42a,b, the plate assembly 42c defines an annular plate chamber 62 that is bound by the core wall 30, the outer annular wall 46c, the plate wall 44f, and the plate wall 44e.
The inner wall 43b is representative of the inner wall 43a. The inner wall 43b is connected to a plurality of the structural members 52, wherein the structural members 52 extend radially from the core wall 30 and are angularly displaced about the longitudinal axis 34. Each of the structural members 52 is similar to but sized differently from the structural members 50. Each of the structural members 52 associated with the inner wall 43b include an inner edge connected to the core wall 30, an opposite outer edge connected to the inner wall 43b, a side edge connected to the plate wall 44e, and an opposite side edge connected to the plate wall 44d. (For example, see the inner edge 54, outer edge 56, side edge 58, and side edge 60 of the structural member 50' in FIG. 7.) Further, and representative of the inner wall 43a, the inner wall 43b defines an intermediate chamber 64 that is bounded by the core wall 30, the inner wall 43b, inner portions of the plate wall 44e, and inner portions of the plate wall 44d. In accordance with the first preferred embodiment of the present invention, each of the plate assemblies 42a-c define plate chambers 62 and each of the inner walls 43a,b define intermediate chambers 64, and all of the chambers 62,64 comprise a filter chamber 66. Stated differently, the filter chamber 66 is defined between the core wall 30 and the filtering surface 40 of the filtering structure 28.
As discussed in greater detail below with reference to a first example of the second preferred embodiment of the present invention, in accordance with the first example of the first preferred embodiment of the present invention, the openings defined through the core wall 30 (for example, see openings 74,76,78 defined through core wall 30' in FIG. 5) are uniquely constructed and arranged so that a substantially controlled inflow distribution, which is preferably uniform, is defined along the length of the internal core tube 26 that is internal to the filtering structure 28. A uniform inflow distribution seeks to, among other things, collect the debris on the filtering surface 40 uniformly, from disk to disk or trough to trough, and thereby allow scaling of test results to strainers with different flow rates and different surface areas. This flow pattern control also seeks to assist in preventing vortexing and air ingestion at the suction strainer 20. In accordance with other examples of the first preferred embodiment, the openings defined through the core wall 30 are constructed and arranged so that the internal core tube 26 does not seek to control the inflow distribution.
FIG. 3 is a schematic, side elevational view of a suction strainer 20' in accordance with a first example of the second preferred embodiment of the present invention. The suction strainer 20' of the first example of the second preferred embodiment is very similar, in general terms, to the suction strainer 20 (FIGS. 1 and 2) of the first example of the first preferred embodiment. Thus, except where specific differences between the suction strainer 20' and the suction strainer 20 are noted or apparent, the following disclosure of the suction strainer 20' should be considered as a supplement to the foregoing disclosure of the suction strainer 20, and visa versa.
In accordance with the second preferred embodiment of the present invention, the internal core tube 26' of the suction strainer 20' is preferably cylindrical and longer than the internal core tube 26 (FIGS. 1 and 2) of the first embodiment. Further, the suction strainer 20' includes more inner walls 43'a-e and plate assemblies 42'a-f than the suction strainer 20 (FIGS. 1 and 2) of the first preferred embodiment. The plate assemblies 42'a-f include plate walls 44'a-l. The inner walls 43'a-e and plate assemblies 42'a-f preferably encircle the internal core tube 26', as is indicated by the broken line showing of the internal core tube 26'. FIG. 3 is schematic in nature because, while the inner walls 43'a-e and plate assemblies 42'a-f preferably define a multiplicity of apertures therethrough, those apertures are not depicted in FIG. 3 in an effort to clarify the view. In accordance with the second preferred embodiment of the present invention, the internal core tube 26' is preferably in the general form of a cylinder that structurally reinforces exterior filtering structure 28'.
In accordance with the second preferred embodiment of the present invention, the suction strainer 20' defines an overall length that is represented by the dimension "a". The core wall 30' defines a first length that does not define openings 74,76,78 (FIG. 5) therethrough, and that first length is represented by the dimension "b". The core wall 30' further defines a second length, represented by the dimension "c", that does define openings 74,76,78 (FIG. 5) therethrough and that is surrounded by the plate assemblies 42'a-f and the inner walls 43'a-e. A separation distance, represented by the dimension "d", is defined between each of the plate assemblies 42'a-f. Also, each of the plate assemblies 42'a-f individually define a thickness that is represented by the dimension "e". The internal core tube 26', inner walls 43'a-e, and plate assemblies 42'a-f define diameters that are represented by the dimensions "f", "g", and "h", respectively. In accordance with one acceptable example of the second preferred embodiments, and in approximation, the dimension "a" is acceptably 36.0 inches, the dimension "b" is acceptably 3.375 inches, the dimension "c" is acceptably 29.875 inches, the dimension "d" is acceptably 2.0 inches, the dimension "e" is acceptably 3.313 inches, the dimension "f" is acceptably 24.0 inches, the dimension "g" is acceptably 26.0 inches, and the dimension "h" is acceptably 42.0 inches.
As suggested by the broken line showing of the core wall 30' in FIG. 3, in accordance with the second preferred embodiment of the present invention, each of the plate walls 44'a-k defines a centered plate hole 48 (FIG. 6) therethrough. The internal core tube 26' extends through the plate holes 48. As an exception, however, the plate wall 44'l does not define such a hole 48 and therefore covers the upstream end 22' of the internal core tube 26' and the core chamber (for example see the core chamber 32 of FIGS. 1 and 2). The plate wall 44'l is more fully depicted in FIG. 4, which is a schematic, upstream end, elevational view of the suction strainer 20', in accordance with the first example of the second preferred embodiment of the present invention. The fact that the plate wall 44'l covers the upstream end 22' of the internal core tube 26' is indicated by the broken line showing of the core wall 30' in FIG. 4.
In accordance with the second preferred embodiment of the present invention, each of the plate assemblies 42'a-f (FIG. 3) include a plurality of structural members 50' therein; and the arrangement and configuration of the structural members 50' within the plate assembly 42'f is representative of the configuration and arrangement of the structural members 50' within each of the plate assemblies 42'a-e. As indicated by the broken line showing of the structural members 50' in FIG. 4, the structural members 50' extend radially from and are angularly displaced about the internal core tube 26'. In accordance with the second preferred embodiment, an identical angle "φ" is defined between each adjacent structural member 50', and one acceptable example of the angle "φ" is 60 degrees. In accordance with the second preferred embodiment of the present invention, the inner walls 43'a-e are not reinforced by structural components that correspond to the structural members 52 (FIG. 2) of the first preferred embodiment. However, in accordance with alternate embodiments of the present invention the inner walls 43'a-e are reinforced by structural components that correspond to the structural members 52 (FIG. 2) of the first preferred embodiment.
FIG. 5 is an isolated, plan view of the core wall 30' in accordance with the first example of the second preferred embodiment of the present invention, wherein the core wall 30' is in an unrolled and flattened configuration. The core wall 30' includes opposite wall edges 68,70 that are preferably joined together in a manner that creates the cylindrical internal core tube 26' (FIG. 3). The internal core tube 26' further includes an upstream edge 71 to which the plate wall 44'l (FIGS. 3 and 4) is affixed. Broken lines 72a-k are included in FIG. 5 for explanatory purposes only. The lines 72a-k represent the points at which the inner peripheral edges 73 (FIG. 6) of the plate walls 44a-k (FIG. 3), respectively, contact the core wall 30' when the plate walls 44a-k are properly installed on the cylindrical internal core tube 26' (FIG. 3).
In accordance with the first example of the second preferred embodiment of the present invention, the openings 74,76,78, only a few of which are specifically pointed out in FIG. 5 in an effort to clarify the view, are in the form of circular holes which extend through the core wall 30'. Also, in accordance with the second preferred embodiment of the present invention, open areas are defined through the core wall 30' by virtue of the openings 74,76,78. Each individual opening 74,76,78 represents or defines an open area. The open area of an individual opening 74,76,78 is representative of the capacity of that individual opening 74,76,78 to pass liquid. Thus, the open area can acceptably be measured perpendicular to the direction of liquid flow through the most restrictive portion of an opening 74,76,78. In accordance with the first example of the second preferred embodiment of the present invention, the openings 78 are the only type of openings defined between the lines 72h and the upstream end 22' of the core wall 30', the openings 76 are the only type of openings defined between the lines 72d,h, and the openings 74 are the only type of openings defined between the lines 72a,d.
Unit areas consisting of a portion of the core wall 30' can be considered to define open areas, wherein the open area of a unit area is the summation all of the individual open areas defined within that unit area. Accordingly, and for example and not limitation, a plurality of core units can be defined as extending sequentially along the length of the internal core tube 26' (FIG. 3). In accordance with one acceptable example of such a sequential arrangement of core units, a first unit of the plurality of units can acceptably and hypothetically be identified as being that portion of the core wall 30' defined between the lines 72b,d. That first unit defines a first unit open area equal to the summation of the open areas of each of the openings 74 defined between the lines 72b,d. Similarly, a second unit of the plurality of units can acceptably and hypothetically be identified as being that portion of the core wall 30' defined between the lines 72d,f. That second unit defines a second unit open area equal to the summation of the open areas of each of the openings 76 defined between the lines 72d,f. In accordance with the first example of the second preferred embodiment of the present invention, the first unit open area is smaller than the second unit open area such that when a pump draws liquid through the wall 30' of the internal core tube 26' (FIG. 3), the flow (i.e., inflow) of liquid through the first unit is substantially similar to the inflow of liquid through the second unit. The lines 72a-k are used in the foregoing example only because they aid in the explanation of the concept of core units. The lines 72a-k are not intended to and should not limit the hypothetical configuration of core units. Core units can be conceptualized and defined without any reference to the lines 72a-k. For example and not limitation, it is acceptable for the edge of a core unit to be located at any location between neighboring lines 72.
As evidenced by the foregoing, in accordance with the first example of the second preferred embodiment of the present invention, the openings 74,76,78 are constructed and arranged such that less open area is defined near the downstream end 24' (FIG. 3) than the upstream end 22' (FIG. 3). Thus, when liquid is drawn into the core chamber (for example see the core chamber 32 of FIGS. 1 and 2) by a pump or the like, a substantially uniform flow (i.e., inflow) distribution is defined along the length of the internal core tube 26' (FIG. 3). In accordance with the first example of the second preferred embodiment of the present invention, the variation in open area of the core wall 30' (e.g., the variation in the open area of the internal core tube 26') is achieved by varying the sizing of the openings 74,76,78. In other words, in accordance with the first example of the second preferred embodiment of the present invention, the pattern of the openings 74,76,78 does not vary significantly along the length of the core wall 30'. More particularly, the opening pattern defined between the lines 72a,b is repeated between the lines 72c,d, the lines 72e,f, the lines 72g,h, the lines 72i,j, and the line 72k and the upstream end 22' of the core wall 30'. Similarly, the opening pattern defined between the lines 72b,c is repeated between the lines 72d,e, the lines 72f,g, the lines 72h,i, and the lines 72j,k. Accordingly, in accordance with the first example of the second preferred embodiment of the present invention, the variation in open area is achieved by virtue of the fact that the openings 78 (which are preferably the only type of openings defined between the lines 72h and the upstream end 22' of the core wall 30') are larger than the openings 74; and the openings 74 (which are preferably the only type of openings defined between the lines 72d,h) are larger than the openings 72 (which are preferably the only type of openings defined between the lines 72a,d). In accordance with first example of the second preferred embodiment of the present invention, each of the openings 74 acceptably defines a diameter of approximately 0.875 inches, each of the openings 76 defines a diameter of approximately 1.063 inches, and each of the openings 78 defines a diameter of approximately 1.25 inches. Also in accordance with the first example of the second preferred embodiment of the present invention, the core wall 30' is acceptably constructed from a sheet of steel such as, but not limited to, a piece of quarter inch coated A36 carbon or uncoated stainless steel.
As mentioned above, in accordance with the first example of the second preferred embodiment of the present invention the variations in open area along the length of the internal core tube 26' (FIGS. 3 and 4) are established by repeating the pattern of openings but varying the size of the openings defined through the core wall 30'. However, in accordance with alternate embodiments of the present invention all of the openings defined through the core wall 30' are the same size, and the variations in open area along the length of the internal core tube 26' (FIG. 3) are established by varying the pattern of the openings through the core wall 30'. In other words, in accordance with alternate embodiments of the present invention, the variation in open area exists by virtue of the fact that more openings are defined through the core wall 30' proximate to the upstream end 22' (FIG. 3) of the internal core tube 26'. Also, in accordance with other examples of the second preferred embodiment, the open areas through the core wall 30' are substantially uniform along the length of the internal core tube 26', whereby uniform inflow along the length of the internal core tube 26' is not provided.
FIG. 6 is an isolated, schematic, elevational view of a plate wall 44' that is representative of the plate walls 44'a-k (FIG. 3), in accordance with the second preferred embodiment of the present invention. The plate wall 44' includes an outer peripheral edge 47 and an inner peripheral edge 73 that encircles and defines a central plate hole 48. The internal core tube 26' (FIG. 3) extends through the central plate holes 28 of the plate walls 44'a-k (FIG. 3). The plate wall 44' depicted in FIG. 6 is not representative of the plate wall 44l (FIG. 3) because the plate wall 44' does not define a plate hole 48 therethrough, as mentioned above.
FIG. 6 is schematic in nature because each of the plate walls 44'a-l (FIG. 3) define a multiplicity of perforations therethrough that are preferably evenly distributed. The perforations are not clearly shown in FIG. 6 in an effort to clarify the view, however a sampling of the perforations is schematically represented by dots. In accordance with the second preferred embodiment of the present invention, an acceptable size of each individual perforation is within the range of approximately 0.0625 inches to approximately 0.250 inches. In accordance with one acceptable example, the perforations are so sized and so numerous that each of the plate walls 44'a-l is approximately forty percent open area. Also, the plate walls 44'a-l are acceptably constructed from a material such as, but not limited to, eleven gauge carbon or stainless steel. In accordance with an alternate embodiment of the present invention, the portion of the plate wall 44'l (FIG. 3) that covers the upstream end of the core chamber (for example see core chamber 32 in FIG. 2) is not perforated.
The term "percent open area" as used within this disclosure can be explained with reference to the plate wall 44'. For example, before the plate wall 44' is perforated it is zero percent open, whereas after the plate wall 44' is perforated it includes a multiplicity of perforations such that the plate wall 44' defines an open area. Each individual perforation represents or defines an open area which is representative of the capacity of that perforation to pass liquid, as discussed above. Further, unit areas consisting of a portion of the plate wall 44' can be considered to define an open area, wherein the open area of a unit area is the summation all of the individual open areas defined within that unit area. For example, if a one square inch surface area of the plate wall 44' is identified before the plate wall 44' is perforated, that square inch surface area is zero percent open. After the plate wall 44' is perforated and that one square inch surface area includes a plurality of perforations therethrough, that square inch surface area is some percent open. If the sum of all of the open areas in that one square inch surface add up to an area of 0.4 square inches, then that square inch surface area is forty percent open. If the entire plate wall 44' is perforated in a manner substantially similar to that one square inch, the plate wall 44' is forty percent open.
FIG. 7 is an isolated, elevational view of a structural member 50' in accordance with the second preferred embodiment of the present invention. In accordance with the second preferred embodiment of the present invention, the structural members 50' are solid. In accordance with the second preferred embodiment of the present invention, the solid structural members 50' function to both structurally reinforce the filtering structure 28' (FIG. 3) and prevent vortexing. In accordance with alternate embodiments of the present invention, a plurality of holes are defined through the structural members 50'. The holes seek to equalize flow within the filter chamber (for example, see the filter chamber 66 in FIG. 2).
In accordance with the second preferred embodiment of the present invention, structural members 50' are incorporated into each of the plate assemblies 42'a-f (FIG. 3). Each of the structural members 50' extends radially from the core wall 30' (FIG. 3). Further, structural members 50' within a single plate assembly 42' are, in accordance with the second preferred embodiment, angularly displaced about the longitudinal axis 34' (FIG. 3) as depicted in FIG. 4. In accordance with various alternate embodiments of the present invention, each plate assembly 42' preferably includes six or more structural members 50' angularly displaced about the longitudinal axis 34'. Each of the structural members 50' includes an inner edge 54 connected to the internal core tube 26' (FIG. 3), an opposite outer edge 56 connected to the respective outer wall 46' (FIG. 3), a side edge 58 connected to the one plate wall 44' (FIGS. 3 and 6), and an opposite side edge 60 connected to another plate wall 44'. In accordance with the second preferred embodiment of the present invention the structural members 50' are acceptably constructed from a sheet of steel such as, but not limited to, a piece of eighth-inch carbon or stainless steel. In accordance with the second preferred embodiment of the present invention, structural members 52 (FIG. 2) are not employed. In accordance with an alternate embodiment of the present invention, structural members 52 are employed.
FIG. 8 is an isolated, schematic, plan view of an representative outer wall 46' of a plate assembly 42' (FIG. 3), wherein the outer wall 46' is in an unrolled and flattened configuration in accordance with the second preferred embodiment of the present invention. The outer wall 46' includes opposite short edges 80,82 that are preferably connected such that the outer wall 46' encircles the longitudinal axis 34' (FIG. 3). The outer wall 46' further includes opposite elongated side edges 84,86. In a representative plate assembly 42' (FIG. 3), the elongated edge 84 of the outer wall 46' is connected to the outer peripheral edge 47 (FIG. 6) of one of the plate walls 44', and the other elongated edge 86 of the outer wall 46' is connected to the outer peripheral edge 47 of the other plate wall 44'.
FIG. 9 is an isolated, schematic, plan view a representative inner wall 43' of the suction strainer 20' (FIG. 3), wherein the inner wall 43' is in an unrolled and flattened configuration in accordance with the second preferred embodiment of the present invention. The inner wall 43' includes opposite short edges 88,90 that are preferably connected such that the inner wall 43' encircles the longitudinal axis 34' (FIG. 3). The inner wall 43' further includes opposite elongated edges 92,94. With respect to an exemplary inner wall 43', the elongated edge 92 is connected to one plate wall 44' (FIG. 3) while the other elongated edge 94 is connected to another plate wall 44'.
FIGS. 8 and 9 are schematic in nature because each of walls 43',46' define a multiplicity of perforations therethrough that are preferably evenly distributed. The perforations are not clearly shown in FIGS. 8 and 9 for the sake of clarity, however a sampling of the perforations is schematically represented by dots. In accordance with the second preferred embodiment of the present invention, and with respect to the inner walls 43'a-e (FIG. 3) and outer walls 46'a-f (FIG. 3), an acceptable size for each individual perforation is within the range of approximately 0.0625 inches to approximately 0.125 inches. In accordance with one acceptable example, the perforations through the walls 43'a-e,46'a-f are so sized and so numerous that each of the walls 43'a-e,46'a-f are approximately forty percent open. In accordance with the second preferred embodiment of the present invention, the walls 43',46' are acceptably constructed, for example and not limitation, from a sheet of metal such as, but not limited to, a piece of eleven gauge carbon or stainless steel. In accordance with alternate embodiments of the present invention, the walls 43'a-e,46'a-f are acceptably constructed, for example and not limitation, from wire wrapped well screen.
Referring to FIG. 10, which is a schematic representation of portions of a BWR nuclear power plant, in accordance with the preferred embodiments of the present invention, the suction strainer 20 (FIGS. 1 and 2) and the suction strainer 20' (FIGS. 3 and 4) are preferably connected to an ECCS of a BWR nuclear power plant. FIG. 10 depicts a portion of an ECCS following a LOCA. The suction strainer 20 is submerged in a suppression pool 100, where the suction strainer 20 is connected to the downstream end of a suction line 102 through which an ECCS pump 104 draws water 105 from the suppression pool 100. In one mode of operation (which is generally depicted in FIG. 10), the ECCS pump 104 discharges through a discharge line 106 to a reactor core 108. In another mode of operation, the ECCS pump 104 discharges back to the suppression pool 100. The suction strainers 20,20' are uniquely constructed and arranged, and operate, such that they are capable of being readily incorporated into, optimize the operation of, and are capable of withstanding the rigors associated with, ECCSs.
It should be understood that the specific construction and arrangements of the suction strainer 20 (FIGS. 1 and 2) and the suction strainer 20' (FIGS. 3 and 4) are provided as acceptable examples only. The broad concepts disclosed with respect to the suction strainer 20 and the suction strainer 20' lend themselves to a variety of differently configured suction strainers, and configurations will vary depending upon desired flow rates, space constraints, and the hydrodynamic forces that a particular suction strainer and the attachment ECCS piping will be potentially subjected to. For example, FIG. 11 is a schematic, side elevational view of a suction strainer 20" in accordance with an alternate embodiment of the present invention. The suction strainer 20" depicted in FIG. 11 is substantially similar to the suction strainer 20' of the second preferred embodiment, except that it includes less plate assemblies 42"a-d, and the diameters of the plate assemblies 42"a-d taper. As another example, FIG. 12 is a schematic, upstream end, elevational view of a suction strainer 20'", in accordance with another alternate embodiment of the present invention. FIG. 13 is a schematic, side elevational view of the suction strainer 20'" of FIG. 12. The suction strainer 20'" depicted in FIGS. 12 and 13 is substantially similar to the suction strainer 20' of the second preferred embodiment, except that the suction strainer 20'" includes less plate assemblies 42"a-d, and the plate assemblies 42'"a-d are starshaped. The plate assemblies 42'" encircle the internal core tube 26", as is indicated by the broken line showing of the internal core tube 26" and core wall 30" in FIG. 12.
As an additional example, another embodiment of the present invention includes a convertible suction strainer (not shown) that includes a 170 square foot filtering surface (for example see the filtering surface 40 in FIGS. 1 and 2), 13 disks (for example see the plate assemblies 42 in FIGS. 1 and 2) that are 40 inches in diameter, and a 24 inch flange (for example see the connection flange 38 of FIG. 1), wherein the convertible suction strainer is 48 inches long from the first to the last disk. The internal core tube (for example see the internal core tube 26 in FIGS. 1 and 2) of the convertible suction strainer has large evenly spaced holes therethrough that are not constructed and arranged to control inflow through the internal core tube. The internal core tube of the convertible suction strainer is constructed and arranged to structurally support a filtering structure (for example see the filtering structure 28 in FIGS. 1 and 2) that is connected to and extends radially from the internal core tube. The downstream end of the internal core tube of the convertible suction strainer is covered with a perforated plate (for example see the plate wall 44'l in FIG. 3) that can be temporarily opened to provide an opening to the core chamber that is defined by the internal core tube (i.e., the first internal core tube). A second internal core tube is capable of being inserted through the provided opening so that it is installed within the core chamber of the first internal core tube. The second internal core tube is constructed and arranged to control the inflow of water, in the manner discussed above, such that substantially even inflow is established along the length of the first internal core tube.
While the embodiments of the present invention which have been disclosed herein are the preferred forms, other embodiments of the method and apparatus of the present invention will suggest themselves to persons skilled in the art in view of this disclosure. Therefore, it will be understood that variations and modifications can be effected within the spirit and scope of the invention and that the scope of the present invention should only be limited by the claims below. It is also understood that any relative relationships and dimensions shown on the drawings are given as preferred relative relationships and dimensions, but the scope of the invention is not to be limited thereby. | A suction strainer includes a hollow internal core tube and an external filtering surface built around the internal core tube. A plurality of openings are defined through the side wall of the internal core tube core. In some cases the openings through the side wall are constructed and arranged such that there is somewhat less open area near the downstream end than the upstream end of the internal core tube, and the amount of open area tapers between the upstream end and the downstream end. As a result, when liquid is drawn into the internal core tube through the plurality of openings, a substantially uniform inflow distribution may be defined along substantially the entire length of the internal core tube. The internal core tube functions as a rigid structural support for the external filtering surface, enabling the apparatus to withstand post-LOCA hydrodynamic forces. The size of the filtering surface is enlarged by virtue of the fact that the filtering surface defines a plurality of filtering disk assemblies that are connected to and extend radially from the internal core tube. A separation distance is defined between neighboring disk assemblies, and filtering inner walls connect between neighboring disk assemblies and extend around the internal core tube at a radius less than the outermost radius of the disk assemblies. The total flow surface area is increased within a limited geometric profile. This serves to maximize surface area while minimizing post-LOCA reactive forces on attachment ECCS piping in a BWR suppression pool. | 6 |
TECHNICAL FIELD
This invention relates generally to movable barrier operators and more particularly to movable barrier operators having lighting.
BACKGROUND
One of the most basic auxiliary features of a movable barrier operator is the control of lighting in a garage. Over the years, the lighting has been provided by an incandescent lamp installed on the movable barrier operator. In Europe, both line voltage and low voltage incandescent lamps are used. More recently, lamps using other technologies have come into interest. With incandescent lamps, the system requires the ability for the lamp to be replaced due to its low life expectancy.
Replacing lights in a movable barrier operator can be problematic. For example, movable barrier operators are often located high enough above the ground that a person must stand on a ladder to reach the movable barrier operator. Moreover, the use of a socket, as is required with incandescent light bulbs, can require additional wiring and space within the movable barrier operator due to the variations in light bulbs from different manufacturers. Movable barrier operators that use light bulbs having a short lifetime typically need to have sections that can be opened or otherwise moved. For example, a user might have to open a cover to access a light socket to replace a burnt out light bulb. The manufacture and assembly of movable barrier operators having such movable parts relating to light sockets can be complex and extra precision may be required during manufacture and assembly to ensure that the various movable parts fit properly together.
There is a movable barrier system in the art that utilizes incandescent lamps with movable shields in order to direct the light generated by the lamps. The incandescent lamps can be replaced because the shield does not completely cover the lamp. The shield is permanently attached to the movable barrier operator, although it is movable.
Another movable barrier in the art utilizes light emitting diodes (“LEDs”) that are mounted onto a metal plate to dissipate heat generated by the LEDs. However, this system can overheat due to the power required to get adequate lighting, when a large number of LEDs (as may be useful or necessary to ensure the provision of a suitable quantity of light) are mounted onto the heat plate, resulting in subpar performance that may damage some of the LEDs.
SUMMARY OF THE INVENTION
An embodiment of the present invention is directed a barrier movement operator for controlling movement of a movable barrier. A head unit includes a chassis and commands the movable barrier to perform movable barrier functions. A plurality of closely mounted light emitting elements is fixedly mounted onto the head unit. A heat sink is in thermal communication with the set of light emitting elements and with the chassis of the barrier movement operator to dissipate thermal energy from the set of light emitting elements. A controller is utilized to control the head unit to provide power to the set of light emitting elements.
By one approach, the light emitting elements may be closely mounted to one another to generate a bright light source. This can be useful when the light emitting elements are LEDs, as they may each individually produce a bright point of light that by itself might not provide sufficient light to illuminate a garage or other enclosure in which the movable barrier operator is mounted. A combination of a plurality of close mounted light emitting elements, however, can be sufficient to illuminate such a space. Furthermore, in the event that one of the light emitting elements malfunctions or is otherwise faulty, a bright beam of light can still be produced by the other adjacent light emitting elements.
These teachings will accommodate the use of light emitting elements that are of the type that are long-lasting and do not require a socket. By using long-lasting socket-less light emitting elements, such light emitting elements can be fixedly or permanently installed in the movable barrier operator. Using such permanently installed light emitting elements can provide numerous benefits. For example, manufacture and assembly of the movable barrier operator may be easier because certain movable parts are not required because there is no need to periodically change the light emitting elements.
The use of closely mounted light emitting elements may generate a relatively substantial amount of heat that can adversely affect the functioning of the light emitting elements. By one approach, the light emitting elements can be mounted onto a plate that serves, in turn, to dissipate such thermal energy. If desired, the plate itself can be in thermal communication with the chassis of the movable barrier operator to further dissipate the heat generated by the light emitting elements. So configured, the chassis can aid in dissipating enough heat to ensure proper operation of the light emitting elements.
These teachings will accommodate an embodiment that is directed to a barrier movement operator for controlling movement of a movable barrier. A head unit of such an operator can comprise a chassis and can serve to command a given movable barrier to perform movable barrier functions. In this illustrative example a plurality of Light Emitting Diodes are fixedly mounted onto the head unit. A diffuser can then be fixedly mounted on the head unit to spread light generated by the set of light emitting elements. A controller can be utilized for controlling the head unit to provide power to the set of light emitting elements.
These teachings will also accommodate a method of controlling the provision of power to a plurality of Light Emitting Diodes that are closely and fixedly mounted on a chassis of a head unit of a movable barrier operator that controls movement of a movable barrier. The movable barrier is commanded to perform movable barrier functions. Power is provided to the plurality of Light Emitting Diodes. Thermal energy produced by the plurality of Light Emitting Diodes is dissipated via the chassis. The head unit is controlled to provide power to the plurality of Light Emitting Diodes.
The above summary of the present invention is not intended to represent each embodiment or every aspect of the present invention. The detailed description and Figures will describe many of the embodiments and aspects of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
The above needs are at least partially met through provision of the method and apparatus for remote control described in the following detailed description, particularly when studied in conjunction with the drawings, wherein:
FIG. 1 illustrates a movable barrier operator according to an embodiment of the invention;
FIG. 2 illustrates a head unit of the movable barrier operator according to an embodiment of the invention;
FIG. 3 illustrates a bottom view of the head unit of movable barrier operator according to an embodiment of the invention;
FIG. 4 illustrates a side view of the head unit according to an embodiment of the invention;
FIG. 5 illustrates a side view of a head unit having reflectors according to an embodiment of the invention;
FIG. 6 illustrates a side view of a head unit having reflectors and diffusers according to an embodiment of the invention; and
FIG. 7 illustrates a side view of a head unit having lenses for directing light generated by permanently mounted light emitting elements according to an embodiment of the invention.
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 various embodiments of the present invention. Also, common but well-understood elements that are useful or necessary in a commercially feasible embodiment are typically not depicted in order to facilitate a less obstructed view of these various embodiments of the present invention. It will further be appreciated that certain actions and/or steps may be described or depicted in a particular order of occurrence while those skilled in the art will understand that such specificity with respect to sequence is not actually required. It will also be understood that the terms and expressions used herein have the ordinary meaning as is accorded to such terms and expressions with respect to the field of the invention and their corresponding respective areas of inquiry and study except where specific meanings have otherwise been set forth herein.
DETAILED DESCRIPTION
At least one embodiment of the invention is directed to the use of one or more permanently installed light emitting elements for a movable barrier operator. The permanently installed light emitting elements may include light emitting diodes (“LEDs”) or other durable and long-lasting light producing elements. Such LEDs may be expected to have a life expectancy that exceeds that of the movable barrier operator onto which they are installed for many normal application settings.
The use of permanently installed light emitting elements installed within the movable barrier operator affects not only the mounting of the lights themselves, but also the device used to spread the light used in the systems. In a normal movable barrier operator, a light diffuser must be removed or opened whenever a light bulb is being replaced. However, in embodiments discussed below, the diffuser may also be permanently installed.
The permanently installed lights, as discussed herein, include light emitting elements not requiring use of a socket. Sockets are utilized in lighting systems utilizing incandescent light bulbs or other elements that generally have a shorter lifespan than the movable barrier operators into which they inserted. Because the light emitting elements discussed herein have a very long lifespan, they are permanently installed so that they do not need to be replaced. As used herein, then, it will be understood that the expression “permanently installed” or the like refers to an installation that is hardwired and that is effected without the use of a socket or other physical fixture that serves and is intended to serve as a means of permitting anticipated removal, by hand, of a failed light emitting element.
There are a variety of different locations onto which the light emitting elements may be mounted. By one approach, the light emitting elements may be distributed around the body of the movable barrier operator to create an even distribution of light around an enclosure within which the movable barrier operator is mounted, such as a garage.
In some embodiments, bright point sources of light, such as those produced by LEDs, can be irritating to one's eyes. Accordingly, because the point sources are so intense it is beneficial to spread light from the sources out at the movable barrier operator. There are many ways by which to spread the light from point sources. Various reflector, diffusers, and lenses may be used to spread the light, as discussed below with respect to FIGS. 3-7 .
The use of closely mounted light emitting elements may generate a relatively substantial amount of heat that can adversely affect the functioning the light emitting elements. By one approach, then, the light emitting elements are mounted onto one or more heat sinks, such as a plate or plates, to dissipate the thermal energy. The heat sink can itself be in thermal communication with the chassis of the movable barrier operator to further dissipate the heat generated by the light emitting elements. The chassis dissipates enough heat to ensure proper operation of the light emitting elements.
So configured, those skilled in the art will recognize and appreciate that these teachings permit the use of permanently installed light emitting elements with movable barrier operators in an effective manner that ensures both adequate lighting results while also ensuring suitable operating conditions for the light emitting elements themselves. This, in turn, permits the movable barrier operator to be designed and manufactured with simpler form factors and fewer moving parts to thereby achieve higher quality products at lower costs. These teachings also avoid the need for occasional replacement of the light emitting elements and therefore free the end user from this maintenance activity.
These and other benefits may become clearer upon making a thorough review and study of the following detailed description. Referring now to drawings and especially to FIG. 1 , an illustrative example of a movable barrier operator is shown therein. Those skilled in the art will appreciate and recognize that the use of such an example is intended to serve only as an illustrative example and is not intended to serve as an exhaustive or otherwise limiting example in this regard.
The movable barrier operator, in this embodiment a garage door operator 10 , is positioned within a garage 12 . More specifically, it is mounted to a ceiling 14 of the garage 12 for operation, in this embodiment, of a multipanel garage door 16 . The multipanel garage door 16 includes a plurality of rollers 18 rotatably confined within a pair of tracks 20 positioned adjacent to and on opposite sides of an opening 22 for the garage door 16 .
The garage door operator 10 also includes a head unit 24 for providing motion to the garage door 16 via a rail assembly 26 . The head unit 24 is attached to a chassis 82 of the garage door operator 10 . This chassis is usually a metal which covers the entire top surface of the operator. The rail assembly 26 includes a trolley 28 for releasable connection of the head unit 24 to the garage door 16 via an arm 30 . The arm 30 is connected to an upper portion 32 of the garage door 16 for opening and closing it. The trolley 28 is connected to an endless chain to be driven thereby. The chain is driven by a sprocket in the head unit 24 . The sprocket acts as a power takeoff for an electric motor located in the head unit 24 .
The head unit 24 includes a radio frequency receiver 50 , as may best be seen in FIG. 2 , having an antenna 52 associated with it for receiving coded radio frequency transmissions from one or more radio transmitters 53 which may include portable or keyfob transmitters or keypad transmitters. The radio receiver 50 is connected via a line 54 to a microcontroller 56 which interprets signals from the radio receiver 50 as code commands to control other portions of the garage door operator 10 .
A wall control unit 60 communicates over a line 62 with the head unit microcontroller 56 to effect control of a garage door operator motor 70 and light emitting elements 72 via power control logic 74 connected to the microcontroller 56 . The power control logic can control the lighting of the light emitting elements in groups or independently as desired. The entire head unit 24 is powered from a power supply 76 . In addition, the garage door operator 10 includes an obstacle detector 78 , which optically or via an infrared pulsed beam detects when the garage door opening 22 is blocked and signals the microcontroller 56 of the blockage. The microcontroller 56 then causes a reversal or opening of the door 16 . In addition, a position indicator 80 indicates to the head unit microcontroller 56 , through at least part of the travel of the door 16 , the door position so that the microcontroller 56 can control the close position and the open position of the door 16 accurately.
FIG. 3 illustrates a bottom view of the head unit 24 of the movable barrier operator 10 according to one illustrative example. As shown, the head unit 24 includes a heat sink such as a plate 100 or other element onto which a plurality of light emitting elements 102 , such as LEDs are mounted. The light emitting elements 102 are permanently installed onto the plate 100 . For example, the light emitting elements 102 may be installed onto the plate 100 when it is assembled at a factory. The plate 100 may also be mounted onto the head unit 24 at the factory during the manufacturing process. By pre-assembling the plate 100 with the permanently/fixedly mounted light emitting elements 102 , the head unit 24 may be quickly and easily installed at a consumer's garage or other enclosure.
The plate 100 may be formed of a thermally conductive material such as a metal. Those skilled in the art will recognize that a variety of possibilities exist in this regard. Some illustrative examples would comprise, but are not limited to, aluminum and aluminum alloys, copper, and so forth. The light emitting elements 102 may generate enough heat such that the generated heat must be dissipated to avoid damaging the light emitting elements 102 . The plate 100 absorbs/dissipates heat generated by the light emitting elements 102 . It would also be possible to use more than one plate to accommodate, for example, differing form factor requirements as correspond to a given application setting.
In this illustrative example the plate 100 is in thermal communication with a chassis 82 of the movable barrier operator 10 to further dissipate the heat away from the light emitting elements, as shown in FIG. 1 . For example, the plate 100 may be physically joined with a metal chassis 82 to further draw the heat away from the light emitting elements 102 . This thermal connection can also be preformed by utilizing heat pipes (which are sealed tubes containing liquid that travels in a vapor phase to a cooler side of the component where the substance then condenses to repeat the process and are often used as computer heatsinks). By using a thermal coupling to the chassis 82 , a relatively large amount of heat may be dissipated, resulting in efficient operation of the light emitting elements 102 .
FIG. 3 illustrates an embodiment in which ten light emitting elements 102 have been evenly spaced along the plate 100 , and which face generally downwardly when the head unit 24 is mounted onto a ceiling of a garage or other enclosure. Many light emitting elements 102 , such as LEDs, generate a bright point of light that may be irritating or distracting to a driver or other person utilizing the movable barrier operator. Accordingly, a diffuser 104 may optionally be placed at the bottom of the head unit 24 to diffuse the bright points of light generated by the light emitting elements mounted on the plate 100 . The diffuser 104 may have a creamy white color in some embodiments. In other embodiments the diffuser may be tinted to modify the color of the light and in still other embodiments the diffuser can be clear albeit with controlled imperfections (such as bubbles in the plastic). The diffuser 104 is shown with dashed lines in FIG. 3 . It may be noted that, when provided, this diffuser can be essentially permanently installed such that hinges, latches, and other end-user manipulable mechanisms need not be provided as there is no particular need to provide end-user access to the permanently installed light emitting element.
The diffuser may be mounted above the Light Emitting Diodes and to direct the light in a general direction away from of the Light Emitting Diodes. A second diffuser may be included and mounted below the Light Emitting Diodes to direct the light in a general direction away from the Light Emitting Diodes. The diffuser may also be mounted below the Light Emitting Diodes to direct the light in a general direction away from the Light Emitting Diodes.
FIG. 4 illustrates a side view of the head unit 24 according to an embodiment of the invention. The chassis 82 may be utilized to mount the head unit 24 onto the ceiling of other surface of a garage or other enclosure. Although not shown in this view, the plate 100 illustrated in FIG. 3 is in thermal communication with the chassis 82 to draw heat away from the light emitting elements 102 generating the heat. The chassis 82 may be preformed of a thermally conductive material such as a metal of choice. The aforementioned optional diffuser 104 fits around the bottom of the head unit 24 and diffuses the light generated by the light emitting elements 102 to avoid annoying or distracting anyone looking at the movable barrier operator 10 when in operation.
Although the embodiments shown in FIGS. 3 and 4 illustrate a head unit 24 in which the light emitting elements 102 are disposed on the bottom side of a plate 100 within the head unit 24 and the diffuser 104 resides below the light emitting elements, it should be appreciated that different arrangements of the light emitting elements 102 may be utilized in other embodiments, depending on system and lighting requirements.
FIG. 5 illustrates a side view of a head unit 120 having reflectors 126 according to an embodiment of the invention. The head unit 120 may implement functions similar, or the same, as the head unit 24 described above with respect to FIGS. 1-4 . The head unit 120 includes light emitting elements 122 disposed on opposite sides of a body of the head unit 120 . Each of the light emitting elements 122 may be mounted onto one or more heat sinks or plates capable of conducting heat. The plates may be in thermal communication with the chassis 124 of the movable barrier operator to dissipate heat from the light emitting elements 122 .
Only two light emitting elements 122 are shown in FIG. 5 . However, a person of ordinary skill would readily appreciate that many additional light emitting elements 122 may also be utilized. The light emitting elements 122 may be disposed physically close to each other to concentrate their generated light. Alternatively, the light emitting elements 122 may be spaced apart. In some embodiments, the light emitting elements 122 are disposed only on the sides of the head unit 120 . In other embodiments, the light emitting elements 122 are disposed along more than two sides, such as on all sides of a perimeter of the body of the head unit 120 .
In the embodiment shown in FIG. 5 , reflectors 126 are utilized to spread the light generated by the light emitting elements 122 and to reflect the light back down onto an area near the movable barrier operator, such as the area below the movable barrier operator. In some embodiments, the light emitting elements 122 may face in the direction of the reflectors 126 so that the reflectors 126 spread the reflected light as much as possible. The reflectors 126 may be formed of a reflective material, such as a reflective metal or a mirror.
FIG. 6 illustrates a side view of a head unit 140 having reflectors 142 and diffusers 144 according to an embodiment of the invention. The head unit 140 may implement functions similar, or the same, as the head units 24 and 120 described above with respect to FIGS. 1-5 . The head unit 140 includes light emitting elements 146 disposed on opposite sides of a body of the head unit 140 . Each of the light emitting elements 146 may be mounted onto one or more plates capable of conducting heat. The plates may be in thermal communication with the chassis 148 of the movable barrier operator to dissipate heat from the light emitting elements 146 .
The head unit 140 includes diffusers 144 disposed below the light emitting elements 146 and the reflectors 142 to diffuse the light from the light emitting elements 146 in addition to the light reflected by the reflectors 142 . Only two light emitting elements 146 are shown in FIG. 6 . However, a person of ordinary skill would readily appreciate that many additional light emitting elements may also be utilized. As with the embodiment shown in FIG. 5 , the light emitting elements 146 may be disposed physically close to each other to concentrate their generated light. Alternatively, the light emitting elements 146 may be spaced apart. In some embodiments, the light emitting elements 146 are disposed only on the sides of the head unit 140 . In other embodiments, the light emitting elements are disposed along all sides of a perimeter of the body of the head unit 140 .
FIG. 7 illustrates a side view of a head unit 160 having lenses 162 for directing light generated by permanently mounted light emitting elements 164 according to an embodiment of the invention. Each lens 162 is placed in front of one or more light emitting elements 164 . The lenses 162 are utilized to spread (or to focus) the light generated by the light emitting elements 164 . In the event that the light emitting elements (such as LEDs) generate a bright point of light, the lenses 162 are utilized to spread the light to minimize the chances of a bright point of light being emitted from the head unit that will be distracting or annoying to a driver or other person within or entering the enclosure in which the movable barrier operator is mounted.
Only two light emitting elements 164 are shown in FIG. 7 . However, a person of ordinary skill in the art would readily appreciate that many additional light emitting elements may also be utilized. As with the embodiments shown in FIGS. 5 and 6 , the light emitting elements 164 may be disposed physically close to each other to concentrate their generated light. Alternatively, the light emitting elements 164 may be spaced apart. In some embodiments, the light emitting elements 164 are disposed only on the sides of the head unit 160 . In other embodiments, the light emitting elements 164 are disposed along more than two sides, such as along all sides of a perimeter of the body of the head unit 160 .
It should be appreciated that modifications within the spirit of the invention may be made to the embodiments described above. The head unit may include light emitting elements disposed on three sides of the chassis of the head unit. The set of light emitting elements may alternatively be disposed on the head unit to generate a cone of light beams in less than about a 180 degree arc on a second surface beneath the head unit.
The teachings discussed herein provide for a durable movable barrier operator that can be readily installed by a user. Once installed, the user will generally never have to replace the lights within the movable barrier operator because such lights are permanently installed therein. The permanently installed lights generate heat and are in thermal communication with a chassis of the movable barrier operator to dissipate the generated heat, to ensure proper operation of the permanently installed lights.
Those skilled in the art will recognize that a wide variety of modifications, alterations, and combinations can be made with respect to the above described embodiments without departing from the spirit and scope of the invention, and that such modifications, alterations, and combinations are to be viewed as being within the ambit of the inventive concept. For example, if desired, light emitting elements having differing emitted light colors can be used. By one approach, for example, red lighting might be used under some operating circumstance to avoid impairing an end user's night vision while white lighting is used under other operating circumstances. It would also be possible for the movable barrier operator to monitor ambient temperature conditions local to some or all of the light emitting elements. In such a case, the movable barrier operator could then selectively deactivate one or more of the light emitting elements when that temperature exceeded some threshold value of concern to thereby aid in preserving the long term functionality of the light emitting elements while still preserving some degree of present functionality. | A barrier movement operator controls movement of a movable barrier. The barrier movement operator includes a head unit, including a chassis, for commanding the movable barrier to perform movable barrier functions. A plurality of closely mounted light emitting elements are fixedly mounted onto the head unit. A heat sink is in thermal communication with the set of light emitting elements and with the chassis of the barrier movement operator to dissipate thermal energy from the set of light emitting elements. A controller is utilized for controlling the head unit to provide power to the set of light emitting elements. | 4 |
BRIEF SUMMARY OF THE INVENTION
It is the purpose of this invention to provide a holder for rolls of paper, such as toilet tissue, that is of economical construction and which increases the ease of paper tear-off and of insertion and removal of the roll as compared with conventional paper holders now in use.
The invention accomplishes this purpose by means of a holder that has tracks to rotatably and slidably receive pins on the ends of a paper holding spindle thereby making it very easy to remove the spindle and to insert or remove a roll of paper. The tracks run vertically and permit the weight of a roll mounted on the spindle to hold the bottom of the roll against a lip or surface on the holder and this serves to resist rotation of the roll when a length of paper is removed thereby facilitating tear-off.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of one form of holder embodying the invention, showing it secured to a wall and showing a roll of toilet tissue in perspective;
FIG. 2 is a front elevation of the holder of FIG. 1 with parts broken away;
FIG. 3 is a cross section along the line 3--3 of FIG. 2;
FIG. 4 is a perspective view of another form of holder embodying the invention;
FIG. 5 is a cross section along the line 5--5 of FIG. 4; and
FIG. 6 is a view similar to FIG. 4 but showing a different track structure in a similar form of holder.
DESCRIPTION OF THE INVENTION
The holder 1 may be in the form of a body or frame formed from sheet metal or molded from suitable plastic materials and has a flat back portion 3, a curved bottom portion 5, and a pair of flat side portions 7 and 9 extending at right angles to the back portion 3. End sections of the two side portions 7 and 9 are formed with outwardly extending U-shaped portions 11 and 13, the interiors of which define parallel tracks or slots 15 and 17. The tracks extend vertically and are also slanted so that their bottom ends are closer to the back portion 3 than their top ends.
A cylindrical spindle 19 has pins 21 projecting from opposite ends and the spindle and pins are dimensioned to enable the pins to move freely up and down the tracks 15 and 17. The body 21 of the spindle slidably fits inside the conventional tubular core 23 of the tissue roll 25 and therefore supports it for vertical and rotary movement in the tracks. Preferably, a strip 27 of relatively high friction material (such as rubber, etc.) is secured to the bottom 28 of back portion 3, as by an adhesive, adjacent the end edge 29 of the bottom and provides a lip or support surface against which the bottom of the paper roll 25 is continuously pressed by the force of gravity.
In use, the back 3 of the holder 1 may be secured by screws 31 to the surface of a wall 33. The spindle 19 is projected through the core 23 of a roll 25 and the assembly inserted in the holder by allowing the spindle pins 21 to enter the open top ends (FIG. 1) of the tracks 15 and 17. The roll will seat on strip 27 and its weight will bear against it to resist turning when the projecting end 35 of the roll is pulled sharply to remove it from the roll.
FIGS. 4 and 5 show a holder 101 embodying the invention which is suitable for mounting flush with the surface of a wall 102, the holder having an arcuate body 103 formed of sheet metal or plastic that will fit in a recess in the wall. The body 103 includes a curved back wall 105 and sidewalls 107 and 109 and a flat circumferential mounting flange 111 extending outwardly from the back and sides and integral with the body 103 for engaging the wall surface around the recess to provide a trim mounting. The front edges of the sidewalls 107 and 109 extend vertically and have outwardly extending vertical U-shaped sections 113 formed therein, the insides of which form tracks 115 corresponding to tracks 15 and 17 of holder 1. Slots 117 are formed in the flange 111 and sections 113 to permit insertion of the spindle pins 21 into the tracks. After the spindle with a roll of paper mounted therein is inserted into the tracks, approximately one half of the roll will be in substantially semi-cylindrical chamber 119 formed by the sidewalls and back of the holder and the roll will continuously rest on the bottom of the wall 105 including the lip or support surface 121 at the bottom front of the holder. Thus, the weight of the roll will resist its rotation and that plus the action of the lip 121 will facilitate tear-off of a length of paper from the roll.
In FIG. 6, the holder 201 is substantially the same as holder 101 except for the track construction. In this form the holder also has an arcuate body 203 with a backwall 205 and sidewalls 207 and 209 and a mounting rim 211. The tracks 213 and 215 are formed by insides of Z-shaped strips 217 and 219 which are secured to the face of the rim 211, and which are secured to and extend along approximately one half the height of the rim. The pins at the ends of the spindle can be dropped into the open top ends of the strips 217 and 219. The roll will then continuously rest on the bottom surface or lip 221 of the back wall 205 to facilitate tear-off as described above.
In the holders 1 and 201 the inner edge of the bottom of the holder (i.e., lips 29 and 221) are close enough to the tracks so that the spindle cannot fall out of the holder when the tissue is all used, that is the lips are less than a core radius away from the tracks. In holder 101 the tracks have a bottom but the lip 121 is placed less than a radius away from them so that, like holders 1 and 201, it wll hold the spindle up when the tissue is used. | A holder for rolls of paper, such as toilet tissue, has vertically extending tracks that receive pin ends of a roll holding spindle whereby the weight of the roll and spindle bears against a lip of the holder to hold the roll in place during tear-off of a length of paper. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to the field of coal pulverizer mills and in particular to lubrication of internal bearings located in a gear box of a coal pulverizer mill, especially a B&W MPS-type mill.
2. Description of the Related Art
Coal pulverizer mills are used to grind coal for combustion in industrial power plants. B&W's MPS-type mills are one type of coal pulverizer which have been used for approximately the past thirty years. The B&W MPS mills use a rotating grinding mechanism to crush coal chunks into finer particles for combustion.
The coal grinding mechanism is driven by an electric motor through a gear reducer contained in a gear casing. The bearings inside the gear casing must be lubricated to prevent lock-ups and excessive wear on the bearing surfaces. Lubricating oil is used for this purpose. However, oil leaks at two bearing locations in the gear casing are a recurring problem with these gear casings.
As seen in FIG. 1, a bearing casing 10 has several bearing positions, two of which are known as bearing position four 30 and bearing position five 20 . The oil leaks which occur in these types of bearing casings 10 occur at bearing positions four and five 30 , 20 . FIG. 2 shows a prior art gear casing configuration of the bearing positions 20 , 30 from the side and helps to explain how the oil leaks occur. Each bearing position 20 , 30 has a bearing cartridge 28 , 38 with an annular groove 26 , 36 around its circumference. Oil is supplied to each groove 26 , 36 through oil tube 40 located between the bearing positions 20 , 30 . Oil moves from the grooves 26 , 36 through an opening in the bearing cartridges 28 , 38 into bearing top chambers 22 , 32 of each bearing position 20 , 30 , respectively. To prevent oil from leaking out the top of the gear casing 10 , an O-ring 24 , 34 is provided around the top of each bearing cartridge 28 , 38 above the annular grooves. Unfortunately, over time these O-rings 24 , 34 harden and lose their seal between the gear casing 10 and bearing cartridges 28 , 38 .
Conventionally, this oil leak problem has been solved by stopping oil flow to annular grooves 26 , 36 , redirecting the oil flow from a manifold 200 (not shown in FIG. 2) through a pair of external hoses, connected to covers 21 , 31 and into bearing top chambers 22 , 32 . Several parts are required to effect this alteration to the oil flow path. This solution is not entirely satisfactory since external hoses present in an industrial setting, such as a power plant, are subject to being cut, corroded, crimped or otherwise damaged. Further, due to the complexity of the alteration of the oil flow path involved, it is not uncommon for the alteration to be made incorrectly, which can lead to continued oil leaks and failure of the bearings.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide an improved oil flow path for gear casings of B&W MPS-type pulverizer mills which eliminates many of the disadvantages of the prior solution for preventing oil leaks.
It is a further object of the invention to provide an improved oil flow path which is simplified, located inside the gear casing and eliminates operating oil pressure against O-ring seals, thereby eliminating the possibility of leaks through these seals.
A further object of the invention is to make manufacture of bearing cartridges holding the gear shafts in place simpler by eliminating some machining on the bearing cartridges.
Accordingly, an improved oil flow path is provided through the gear casing of a B&W MPS-type pulverizer mill for the numbers 4 and 5 bearing positions. The improved flow path has bearing cartridges for each bearing position with passageways through the body for delivering oil from an internal supply hose and/or pipe to the bearing top chamber of each bearing position. A swivel fitting is connected to the bottom of each passageway for making the connection to the supply hose and/or pipe.
Alternatively, a simple block connector mounted to the bottom of each passageway may be used in place of the swivel fitting.
The various features of novelty which characterize the invention are pointed out with particularity in the claims annexed to and forming a part of this disclosure. For a better understanding of the invention, its operating advantages and specific objects attained by its uses, reference is made to the accompanying drawings and descriptive matter in which a preferred embodiment of the invention is illustrated.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings:
FIG. 1 is a sectional perspective view of a gear casing used in B&W MPS-type pulverizer mills;
FIG. 2 is an enlarged sectional side elevational view of the number 4 and 5 bearing positions of a prior art configuration of the gear casing in FIG. 1;
FIG. 3 is an enlarged sectional side elevational view of a portion of the number 4 and 5 bearing positions of the gear casing in FIG. 1 having the oil flow path of the present invention;
FIG. 4 is an alternate embodiment of the oil flow path shown in FIG. 3;
FIG. 5 is a third embodiment of the oil flow path shown in FIG. 3;
FIG. 6 is a fourth embodiment of the oil flow path shown in FIG. 3; and
FIG. 7 is a fifth embodiment of the oil flow path shown in FIG. 3 .
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the drawings in which like reference numerals are used to refer to the same or similar elements throughout the several views, FIG. 3 shows bearing positions four and five 20 , 30 respectively, having an improved oil flow path to prevent leaks through the O-rings 24 , 34 . Each bearing position 20 , 30 is provided with a bearing cartridge 29 , 39 designed to improve the oil flow path in the bearing casing 10 by avoiding the O-rings 24 , 34 .
Bearing cartridges 29 , 39 are provided with passages 122 , 132 connecting the bottom edges of the bearing cartridges with the bearing top chambers 22 , 32 , respectively. Swivel connectors 120 , 130 are mounted to the bottom edges of the bearing cartridges 29 , 39 at the ends of the passages 122 , 132 . Swivel connectors 120 , 130 are used to attach oil supply hoses and/or pipes, such as hoses 125 , 135 shown in FIG. 3, to the passages 122 , 132 . Hoses 125 , 135 may be connected to a manifold 200 (not shown in FIG. 3 ).
At time of assembly and disassembly, the sub-assemblies consisting of bearing cartridges 29 , 30 , swivel connectors 120 , 130 and hoses 125 , 135 , must be able to pass through bores in casing 10 . To accomplish this feature, the swivel connectors 120 , 130 and hoses 125 , 135 are turned inward to create an envelope equal to or smaller than the outside diameter of bearing cartridge 29 , 39 . Once each sub-assembly passes through the bores in casing 10 , each swivel connector 120 , 130 , with attached hoses 125 , 135 are turned outward to facilitate assembly.
The swivel connectors 120 , 130 provided at the bottom ends of bearing cartridges 29 , 39 permit oil to pass from the manifold 200 through the respective hoses 125 , 135 , swivel connectors 120 , 130 and passages 122 , 132 into each of the top chambers 22 , 32 , where the oil is used to lubricate the bearing. At no time does the oil being conveyed on this path contact the outside of the bearing cartridges 29 , 39 or O-rings. Thus, pressure against the O-rings 24 , 34 is reduced, thereby reducing wear on the O-rings 24 , 34 and the lack of pressure prevents leaks occurring through the O-ring seals.
Several alternate embodiments for the swivel connectors 120 , 130 and hoses 125 , 135 are envisioned. FIGS. 4-7 display four alternate connections which could be used to provide a path from the manifold 200 to the passages 122 , 132 . In order to simplify the description of each embodiment, only the bottom portion of one bearing cartridge 29 is shown in each figure, although the same or a different embodiment may easily be used on the second bearing cartridge 39 . The remainder of the bearing cartridge 39 which is not shown in these four figures is the same as that of FIG. 3 in each case, except as noted.
FIG. 4 displays an embodiment of the connector in which a swivel connector 120 has a pipe connector 129 which is used to attach a flexible supply hose 126 connected to the manifold 200 .
FIG. 5 has a bearing cartridge 50 with a supporting ledge 55 for supporting a pipe 129 connecting the passage 122 to the manifold 200 . The supporting ledge 55 extends from the inner side of the bearing cartridge 50 underneath the passage 122 , thereby creating a substantially right-angle bend at the bottom end of the bearing cartridge 50 . A flexible hose 190 may be attached to the pipe 129 at any convenient point to place the pipe 129 in communication with the manifold 200 .
In the embodiment of FIG. 6, the swivel connector 120 is replaced by a stationary block 140 which may be bolted to the bearing cartridge 29 . A hose connector 150 attached to the block 140 provides a fitting for a flexible hose 126 connected to the manifold 200 .
Finally, in FIG. 7, the stationary block 140 may be used to support a pipe 128 connected between the passage 122 and the manifold 200 . A flexible hose 190 may connect the pipe 128 to the manifold 200 .
It is envisioned that the swivel connectors 120 , 130 may be mounted to the ends of the passages 122 , 132 in any known manner which permits oil to flow through the connectors 120 , 130 into the passages 122 , 132 . Each swivel connector 120 , 130 or block 140 must be sized appropriately for the limited space available adjacent the bearing cartridges 29 , 39 inside the gear casing 10 as well.
The improved bearing positions 20 , 30 permit the oil path to be kept entirely within the casing 10 , thus reducing the likelihood of oil leaks or external forces causing failures of the oil supply lines. Further, the apparatus required to implement this oil path is relatively simple, with fewer parts, easier assembly and, therefore, less likelihood of incorrect implementation in existing bearing positions.
While a specific embodiment of the invention has been shown and described in detail to illustrate the application of the principles of the invention, it will be understood that the invention may be embodied otherwise without departing from such principles. | An apparatus for modifying a gear casing used in coal pulverizer mills prevents lubricating oil leaks through worn O-rings by redirecting the oil in a different path which does not come into contact with the O-ring seals. An internal hose connection provides oil directly to a bearing top chamber through a passage in the bearing cartridge. A special connector is used to connect the internal hose to the passage. Several connector embodiments are disclosed. | 5 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to flexible pipe joints and more particularly to flow-through swivel pipe joints adapted to perform in an underwater high pressure environment.
2. Description of the Prior Art
Undersea pipe laying operations are important to a number of activities, particularly in the petroleum exploration and production industries. Many offshore oil wells, for example, require a line to be laid from the wellhead to a point at which the production from the well is gathered. One method used to bury a pipeline in a seabed involves towing a specially designed sled along the seabed by means of a tow line attached to a barge positioned on the surface of the water. The sled is positioned around and follows a pipeline which has previously been laid on the seabed. Pumps on the barge supply high pressure water to jetting nozzles mounted on the sled. The nozzles are directed towards the seabed so that the high pressure water stream digs a trench as the sled is towed along the seabed. The pipeline is progressively laid into the trench behind the sled as the trenching operation proceeds across the seabed. One example of such a pipe burying apparatus is disclosed in U.S. Pat. No. 4,041,717.
A high pressure water line is used to convey water from the barge pumps to the jet nozzles on the sled. Because a large amount of relative motion is normally experienced between the sled on the seabed and the barge on the surface of the water, some means of imparting flexibility to the high pressure connection between the barge and the sled should be provided in the system. The water lines themselves may be constructed of flexible material. In addition, it has been found desirable to incorporate a flexible pipe joint into the system to connect the high pressure line to the jet nozzles at the sled. This pipe joint typically includes an inlet passage, which is connected to the high pressure water line from the barge, and two outlet passages, each of which is connected to a conduit through which the high pressure water is conveyed to the jet nozzles.
The performance requirements of such a joint are demanding. It must be tightly sealed so that the high pressure water flowing through the joint may not escape, but the joint must be relatively friction free so as to retain flexibility under severe conditions without experiencing an abnormally short usuable life span. The durability of such a joint is especially important because of the remote undersea location in which it is used, with the consequently high cost of replacing such a joint. These requirements are further complicated by the corrosive salt water environment in which such joints normally are operated.
Flexible joint designs which are adapted to operate under high internal pressure are known in the art. Some such designs utilize a spherical ball and socket type design to give the joint the desired freedom of movement. Such joints typically have pressure balancing devices and are preloaded by using some means to apply opposing forces which clamp the joint around the spherical ball element. The complicated design of such joints, however, makes them unsatisfactory when used in an undersea pipe burying apparatus of the type described above. Such joints typically exhibit an excessive amount of friction in motion, resulting in an abnormally short life span.
Other high pressure joint designs utilize ball bearings in the joint to counteract the adverse effects of a high amount of friction. It has been found, however, that the use of such joints introduces an excessive cost into the pipe burying system. The two outlet passages for such joints are in axial alignment and require that the fixed outlet conduits on the jet sled, to which the joint is connected, also be in axial alignment within close tolerances. It has been found that maintaining these close tolerances during construction of the jet sled is difficult and costly.
Consequently, there is a need for a simple, reliable, and economical flow-through swivel pipe joint design which may be used in high pressure applications.
SUMMARY OF THE INVENTION
A flow-through swivel joint is provided for connecting an inlet line to a pair of fixed, approximately coaxial outlet conduits. The swivel joint includes a body member which defines an inlet passage for connection to an inlet line and a pair of outlet passages whose longitudinal axes are aligned and perpendicular to the longitudinal axis of the inlet passage. An elongate member is positioned within each outlet passage of the body member. Each elongate member has an internal tubular passage for communication with a fixed outlet conduit. A convex spherical surface is disposed proximate one end of each elongate member. A socket member is slidably mounted within each outlet passage and has an internal concave spherical surface which makes mating contact with no more than the outward facing portion of the spherical surface of the corresponding elongate member. A retaining means is provided for slidably fixing the socket members within the outlet passages, thereby retaining the elongate members within the outlet passages.
In a more specific embodiment of the invention, circumferential grooves, which contain sealing rings, are provided on the movable surfaces of the joint, with grease fittings included to provide lubrication to the moving parts of the joint.
It is therefore a feature of this invention to provide a flow-through swivel pipe joint particularly adapted for use in an underwater pipe burying apparatus.
It is another feature of this invention to provide a flow-through swivel pipe joint which exhibits pivotal freedom of movement to facilitate assembly and reduce costs of construction where the components to which the joint is connected cannot be aligned exactly without undue expense.
It is an additional feature of this invention to provide a flow-through swivel pipe joint which may be preloaded to facilitate its use under high pressure conditions.
It is also a feature of this invention to provide a flow-through swivel pipe joint, the inlet of which is rotatable about the longitudinal outlet axis in operation.
It is another feature of this invention to provide a flow-through swivel pipe joint which is self-sealing under high internal pressure conditions.
BRIEF DESCRIPTION OF THE DRAWINGS
A more specific depiction of the invention summarized above is illustrated in the appended drawings, which form a part of the specification. The drawings, however, illustrate only a typical embodiment and should not be considered to limit the scope of the invention.
IN THE DRAWINGS
FIG. 1 is a pictorial representation of the operating environment in which the flow-through swivel joint is utilized.
FIG. 2 is a plan view in partial section of a flow-through swivel joint.
FIG. 3 is a frontal elevation of the jet sled shown in FIG. 1.
FIG. 4 is a plan view of the jet sled shown in FIG. 1.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1, the environment of use for the joint is shown in pictorial representation. A jet sled 10 is towed along the seabed 12 by a tow line 14 attached to a surface vessel (not shown). A flow-through swivel joint 16 is affixed to the sled 10 through two outlet conduits 29, shown in FIG. 2. A high pressure water line 18, providing high pressure water from pumps located on the surface vessel to a plurality of jets 20 on the jet sled, is attached to the inlet passage of swivel joint 16. High pressure water forced through the jets 20 digs a trench in the seabed for the pipeline to be buried.
FIGS. 3 and 4 provide additional views of the jet sled 10 shown in FIG. 1. The swivel joint 16 is affixed to the sled 10 through two outlet conduits 29, which are rigidly mounted with respect to the sled. As the high pressure water line 18 flexes and moves relative to the sled 10, the swivel joint 16 attached to line 18 allows the line to swivel with respect to the outlet conduits 29.
FIG. 2 is a plan view in partial section of the swivel joint of the invention. The flow-through swivel joint 16 includes a body member 22, a pair of elongate members 28, a pair of socket members 32, and a pair of retainer members 38. The inlet passage 24 of the joint is connected to the high pressure water line 18, and each elongate member 28 is connected to an outlet conduit 29, mounted on a jet sled. The outlet conduits 29 are schematically represented by dashed lines.
Although the components of only one of the two outlet portions of the joint will be discussed, it should be understood that the joint illustrated is symmetrical and that, consequently, the description applies equally well to the other outlet portion of the joint. Within the outlet passage 26 is positioned an elongate member 28. The elongate member 28 includes a tubular passage for the flow of fluid therethrough. The outer end of the elongate member 28 is adapted to be permanently affixed, as by welding, to an outlet conduit 29. Disposed on the outer surface of the inner end of the elongate member 28 is a convex spherical surface 30.
The socket member 32 provides a pre-loading adjustment for the joint and provides a bearing surface for the rotational and pivotal motion of the elongate member 28. The socket member 32 is slidably fitted within the outlet passage 26, having an outer cylindrical surface 34 corresponding to the inner cylindrical surface of the outlet passage 26. The inner surface 36 of the socket member 32 is concave spherical in shape. The surface 36 has the same radius of curvature as the convex spherical surface 30 on the elongate member 28, surfaces 30 and 36 thereby being adapted to make mating contact. It is important to note that the spherical surface 36 does not make contact with the innter portion of the spherical surface 30. This limitation is best understood by referring to the imaginary sphere which would be formed by completing surface 30 in all directions. The outer hemisphere of such a sphere may be defined as that hemisphere located on the outlet side of a plane which passes through the center of the sphere and is perpendicular to the longitudinal axis of the outlet passage 26. The spherical surface 36 must make contact with no more than the outer hemisphere of this imaginary sphere; that is, the surface 36 cannot contact any portion of the spherical surface 30 which is coextensive with the inner hemisphere corresponding to this outer hemisphere. This limitation is necessitated by the unique way in which this joint is attached within its operating environment and pre-loaded, as discussed below.
It can be seen that the mating contact between the surfaces 30 and 36 allows the elongate members 28 to freely pivot and rotate with respect to the body member 22. It should also be noted that, when the joint is installed in an environment in which the elongate members 28 are rigidly affixed to structure external of the joint, the body member 22, including the inlet passage 24, is free to rotate about the longitudinal axis of the outlet passages 26.
An externally threaded retainer member 38 screws into an internally threaded portion of the outlet passage 26, thereby retaining the socket member 32 within the outlet passage 26. When the elongate members 28 are each rigidly affixed to structure external of the joint, it can be seen that, as the retainer member 38 is screwed into the outlet passage 26, the wedging effect of the socket member 32 will tend to increase the force with which surface 36 contacts surface 30. In this manner, the pipe joint may be pre-loaded, so that initial pressurization within the joint will not leak out between the surfaces 30 and 36 nor between the surface 34 and the surface of outlet passage 26. When the joint is in operation, the internal fluid pressure acts against the elongate member 28, causing a force to be exerted in the direction of arrow 58. In this manner, the joint is made self-sealing under pressure, as a further means of preventing leakage of the high internal pressure through the movable portions of the joint.
A grease fitting 40 allows lubrication to be applied, through the passages 42 and 44 in the body member 22 and the socket member 32, respectively, to lubricate the bearing surface between the socket member 32 and the elongate member 28, and the sliding surface between the socket member 32 and the body member 22. Grooves 46 in the socket member 32 include seals 48 which provide grease seals to retain grease between the outlet of the body member 22 and the socket member 32. Grooves 50 in the spherical surface of the elongate member 28 include seals 52 which provide a grease seal to retain grease between the elongate member 28 and the socket member 32. A protective cap 54 covers the grease fitting 40 as a means of isolating the grease fitting from the external undersea environment in which the joint is utilized.
To assemble the joint for use in a pipe burying operation, the elongate members 28 are loosely fitted within the outlet passages 26 of the body member 22. The socket members 32 are then placed over the outer ends 56 of the elongate members 28 and slidably fitted within the outlet passages 26. The retainer members 38 are then placed over the outer ends 56 of the elongate members 28 and screwed into the threaded portions of the body member 22 a slight amount. With the joint thus loosely assembled, the outer ends 56 of the elongate members 28 are welded to the outlet conduits 29, which are fixed to the structure of the sled 10. The pivotal feature of the joint design is particularly useful at this point of the assembly. Although the longitudinal axes of the outlet passages 26 of the body member 22 are in coaxial alignment, the longitudinal axes of the outlet conduits 29 are ordinarily not in exact axial alignment, since this cannot be economically achieved with the acceptable construction methods for the sled 10. Since the elongate members 28 can pivot through an angle 62, however, each elongate member 28 may be aligned with its corresponding outlet conduit 29. The elongate members 28 are then welded to the outlet conduits 29. Assembly of the joint may then be completed by tightening the retainer members 38 to the desired torque to achieve proper preloading. Although the longitudinal axes of the elongate members 28 will thus be out of alignment with each other and with the longitudinal axis of the outlet passages 26 of the body member 22, the spherical surface contact between the elongate members 28 and the socket members 32 will permit the body member 22, including the inlet passage 24, to rotate. In operation, variations in the elevation of the seabed surface, ocean currents, wind, and other factors will combine to cause frequent changes in the vertical and horizontal distances separating the surface vessel and the sled 10 on the seabed. As has been shown and described herein, the swivel joint 16 may freely rotate, thereby accommodating these variations without undue wear on the joint itself or on the high pressure water line 18.
It is apparent that a divided flow swivel joint has been described which substantially encompasses the features, objects, and advantages described herein. Although the invention has been described in conjunction with this specific embodiment, it will be understood that the invention is not limited thereto, since many alternatives, modifications, and variations will be apparent to those skilled in the art. For example, a plurality of high pressure water lines may be provided for one sled, with multiple joints on the sled to provide connections between the water lines and the jets of the sled. Accordingly, it is intended that all such other forms of the invention fall with the spirit and scope of the apparatus as described herein. | A high pressure flow-through swivel joint is particularly adapted for connecting high pressure water lines to a jet sled in an underwater pipe burying apparatus. The joint includes mating spherical joint surfaces which allow pivotal adjustment during assembly, in order to compensate for construction tolerances. In addition, the mating spherical surfaces allow rotational freedom for the joint inlet passage when the pipe burying system is in operation. | 4 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This patent application claims the benefit of priority from U.S. Provisional Patent Application Ser. No. 60/497,145 filed on Aug. 22, 2003. This application incorporates by reference the entire disclosure of U.S. Provisional Patent Application Ser. No. 60/497,145.
FIELD OF THE INVENTION
This invention relates to the automated capture and authentication of biometric information, more particularly to a more cost effective biometric pen with improved security features.
BACKGROUND OF THE INVENTION
Many user identification systems are known in the art. The most common method for user identification in typical computer applications is through the use of a user identification and password, often alpha-numeric strings used to verify the user. In other approaches, various methods are employed for storing image or password information in a magnetic stripe or in an optically encoded image or pattern, which is physically part of the identification card. Still other approaches utilize a “smart card” having, for example, its own semiconductor memory capability for information storage.
More elaborate schemes take advantage of the user's unique physical features such as fingerprints, facial features and retinal scan data. Once these features are digitized as an image, the processed data is stored for reference at a later time. When the user logs into the system, then the reference data is compared to the input to determine the similarities.
More recently, there have been developments in the field of automatic signature verification. In the early stages, systems were disclosed which made the concept of personal identification via computer-based signature practical. Subsequently, a number of patents disclosed systems whereby the use of acceleration and pressure data from a person's unique signature dynamics were compared to verify the user's identify. Following are examples of such patents in the prior art.
U.S. Pat. No. 4,513,437 of Chainer, et. al. entitled “Data Input Pen for Signature Verification,” discloses a special structure within the pen for detecting acceleration forces involving variable capacitance transducers and does not disclose nor suggest a cost-effective pen apparatus or a secure method of maintaining the signature data.
U.S. Pat. No. 5,018,208 of Gladstone entitled “Input Device for Dynamic Signature Verification Systems,” discloses a pen with barrel pressure transducers for sensing radially-inward-directed finger pressure against the barrel. However, the patent does not suggest or disclose a cost-effective pen apparatus or a secure method of maintaining the signature data.
U.S. Pat. No. 5,517,579 of Baron, et. al, entitled “Handwriting Input Apparatus for Handwriting Recognition using More Than One Sensing Technique,” discloses a handwriting recognition apparatus employing at least two different sensing techniques and a method by which each handwritten symbol may be recognized using a per-person, per-symbol database. Once again, the patent does not disclose a cost-effective pen apparatus or a secure method of maintaining the signature data.
U.S. Pat. No. 5,774,571 of Marshal entitled “Writing Instrument with Multiple Sensors for Biometric Verification,” discloses an apparatus with a grip sensor that senses the grip pressure pattern of the user and compares those patterns against known patterns. The grip sensor precludes the device from being cost-effective and the patent does not discuss or disclose the security of the data.
U.S. Pat. No. 6,236,740 of Lee entitled “Signature Verification Apparatus and Method Utilizing Relative Angle Measurements,” discloses an apparatus and method for verifying a signature by generating a string of identification digits in a document, writing those identification digits with a data input stylus and verifying the identification digits according to the relative angle of the data input stylus. The patent discloses one method of adding security to the data but does not provide for a cost-effective writing instrument.
U.S. Pat. No. 6,539,101 of Black entitled “Method for Identity Verification,” discloses a verification method whereby the user grasps a writing stylus that captures a fingerprint image and compares that image against a known image. Once again, the finger-print gathering apparatus on the barrel of the pen makes the device cost-prohibitive and there is no method disclosed for preserving the security of the data.
As can be seen from the foregoing, the configuration of each of the devices causes them to be considerably more costly than a conventional writing instrument. In addition, another significant problem is that both the input data and the reference data can be easily stolen and used by unauthorized parties. Therefore, a need remains for a cost-effective writing device that is capable of providing secure biometric information for verification.
SUMMARY OF THE INVENTION
This present invention includes a method for capturing and transmitting data captured from a writing instrument in a secure manner. More specifically, the biometric information collected from the pen is coupled with at least one additional data point for encryption. The user initially uses the pen to create a signature which is converted into an encrypted reference value in accordance with the present invention and stored for later use. When authentication is desired, the user uses the same or similar pen to create a signature which again is converted into an encrypted data value. Thereafter, the encrypted reference value is compared to the encrypted data value to determine if the values substantially match. There is not need to retain the original reference signature, thereby enhancing the security of the overall system.
This invention, together with the additional features and advantages thereof will become more apparent to those of skill in the art upon reading the description of the preferred embodiments, with reference to the following drawings.
DESCRIPTION OF THE DRAWINGS
A better understanding of the system and method of the present invention may be had by reference to the drawing figures, wherein:
FIG. 1 shows a top view with the outer casing partly broken away of the pen incorporating the features of the present invention;
FIG. 2 shows a frontal view of an alternative embodiment of the pen in cross-section;
FIG. 3 shows a side view of the same alternative embodiment of the pen in cross-section; and
FIG. 4 is a flow diagram showing certain security features of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention is an improved device for verifying the identity of the user. As used herein unless the context indicates otherwise, a “pen” is any device that is compatible with either the hand or finger of the user for purposes of making a notation. While the drawings depict a conventional shape of a pen, other shapes and designs are also included within the scope of the present invention such as any attachment to a finger or any implement that can be held with a hand for such purpose. It will be understood by one skilled in the art that it is not necessary to use precisely the same type of pen as hereinafter described, or even to have an actual mark made at all. In fact, for certain secrecy applications the latter might be desired. For convenience of reference in the subsequent description, the overall apparatus will simply be referred to as a pen.
Also as used herein unless the context indicates otherwise, “biometric information” means information relating to the characteristics of the user when using the pen such as, for example, the angle at which the pen is tilted, the pressure applied by the pen to the writing surface, the speed at which the signature is written and other such characteristics. For convenience of reference in the subsequent description, the overall collection of information will simply be referred to as biometric information.
The pen 102 of the present invention has numerous uses, and primarily for purposes of illustration, include signature verification at POS terminals, pen-based computers user identification, and to provide improved convenience to guests within various controlled environments. It should be appreciated that the present invention may be used in a number of different applications and in a number of different industries.
Referring now to the various figures of the drawing wherein like reference characters refer to like parts throughout the several views. FIG. 1 is a top view with the outer casing partly broken away of the pen incorporating the features of the present invention.
In FIG. 1 , the overall structure of the pen 102 includes an outer casing 103 constructed of a rigid or semi-rigid material such as plastic, metal, or the like. The outer casing 103 is preferably tubular, however the cross-section of the tube may be circular, triangular or other configurations which may improve the comfort of the grip or the functionality of the device. In addition, the outer casing 103 may be constructed of a conductive material so as to shield the circuitry inside the casing 103 from electromagnetic noise.
The distal end 106 of the pen 102 may be adapted to receive a connector 104 , which connects the pen to a data acquisition device. The connector may be a USB cable, a firewire cable or any other connection to a data acquisition device, including a wireless connection as will be discussed later. Alternatively, the pen 102 may be configured with a socket capable of accommodating a connector 104 so that the user may carry the pen 102 with them and connect it to the connector 104 only when necessary. The circuit board is coupled with certain electronics, such as motion sensors 107 , used in capturing data. Adjacent to the connector 104 at the distal end 106 of the pen 102 is a circuit board containing, among other things, a micro-controller 108 . The micro-controller 108 serves a number of functions relative to data security which will be discussed later. First, it identifies each ball point cartridge 110 as a unique cartridge. Second, it collects data from the sensors 107 and communicates the data through the connector 104 to the data acquisition device. Third, it provides a time stamp of the time and date the data was collected from the sensors 107 and encrypts the identity of the cartridge 110 , the data and the time stamp so as to create a unique and highly secure set of test data.
A removable grip 112 is located at the proximal end 105 of the pen 102 . The removable grip 112 may be any removable grip commonly found at office supply outlets. Alternatively, the removable grip 112 may be specially constructed of any material such as plastic, rubber or the like and may be constructed of a material and in a configuration to maximize the user's comfort. If the removable grip 112 becomes soiled or worn, it may be removed and replaced with a new one.
Also at the proximal end 105 of the pen 102 is a standard ball point cartridge 110 which is coupled with the casing 103 by threads, a snap-in mechanism or the like. More specifically, the casing 103 is configured to accept cartridges 110 such as those that are commonly found at an office supply outlet. If the pen 102 runs out of ink, a new cartridge 110 may be substituted. Additionally, the cartridge 110 can be made of a plastic stylus or other custom tip as applications may require. In addition, the overall pen structure has been embodied in a device substantially the same size as a conventional ball point pen so that the user may grip and write with the pen 102 in any manner the user desires. This is important because the user is not required to hold the pen 102 in a certain way in order to properly record data. While the “stylus” type devices known in the prior art do not require the user to hold the pen in a certain way, these devices are used with electronic pads or tablets. Typical pen-type devices known in the prior art that do not require writing pads or tablets require the pen to be gripped in a specific configuration in order to properly collect data.
FIG. 2 and FIG. 3 show front and lateral views, respectively, of a pen 102 of the present invention in a charging cradle 120 . In this configuration, the pen 102 is shown without a connector 104 attached. Instead, the pen 102 is configured with a radio frequency, or RF, transmitter 126 capable of transmitting data from the pen 102 to the RF receiver 124 located in the charging cradle 120 . The absence of the connector 104 makes characteristics of the pen 102 substantially more similar to a standard ball point pen and, therefore, should provide more reliable data for comparison. Because the RF transmitter 126 will need power transmit the signal to the RF receiver 124 , the pen 102 is configured with a rechargeable battery 128 . The rechargeable battery 128 can be recharged when in the charging cradle 120 using, for example, induction charging. By using an inductive transfer coil 123 in the charging cradle 120 and an embedded inductive charging coil 121 inside the pen, the pen outer casing will not have any exposed connectors for charging. This causes the pen to look and feel like a normal pen when writing and the user does not need to be concerned about touching electrical contacts when using the pen.
The identity verification system of the present invention can be used in a variety of applications requiring identity verification. Examples of applications for the present invention include law enforcement; voter registration and confirmation; drivers' license registration and verification; and credit card verification. In a typical application, a sample signature is recorded for reference purposes at a time that the identity of the user can be verified. The reference signature is then stored for comparison at a later time.
At such time as the user desires to be authenticated, the user can use the pen 102 to sign in the same manner as when the user signed the reference signature. It is important to note that the “signature” need not be the person's name but may be a password or secret word or phrase known only to the user. In addition, it is not necessary for the user to actually “write” anything in the sense that the user is making a marking on paper. The user could simply make a motion in the air. The system will then match the signature to be authenticated with the reference signature to determine if the user is authenticated.
As can be seen from FIG. 4 , the security of the data transmitted for verification is one aspect of the present invention. First, biometric information 200 is collected from a number of different sources. Data 201 is collected from sensing the force and movement of the cartridge 110 . As described above, the fact that the cartridge 110 and the replaceable grip 112 can be easily substituted allows the user to use the pen in any way the user desires. Accordingly, all users in a common environment may use a common pen or each user can use a different pen 102 , in which case the cartridge and pen sensors can be associated with that user's signature. In this way, a pen may be used by a number of different users in a common environment or, for greater security, by a single user.
Biometric information 200 is also collected in the form of the alpha-numeric sequence generated 202 . The user can use his or her name or any variant thereof (e.g. John Quincy Smith, John Q. Smith, J. Q. Smith, etc.) or any alpha-numeric string (e.g. Mickey mouse, July eleventh, etc.) as the user's “signature.” In addition, biometric information is collected from the motion sensors 203 within the pen 102 when the reference signature is created. It is important to recognize that conventional biometric writing authentication systems only collect and compare data from the sensors for comparison.
The data is aggregated to form a complete set of reference data 204 which is then encrypted 205 to create the encrypted reference data 206 . This reference data can be used immediately or can be stored in a normal medium 207 such as a server hard-drive, magnetic strip of smart-card for later use. The encryption processing method involves the phase preservation and reconstruction method similar to holographic recordings. Both the amplitude and phase of the pen movement are recorded. Once this information is digitized, the reference strokes (such as signature, ID phrase or password) are then correlated with the object signal form (created by the verifying entity such as banks or any organization providing the service). Once these two signals are multiplied (in complex domain), then the resulting data will be a “digital hologram” of the signature (i.e. multiplication of two waveforms with complex amplitude and phase preserved). This digital hologram can be easily stored and copied. However, it is not useful for anything until it is “de-convoluted” in the complex domain (multiplied in the Fourier frequency domain) with the original phase of the input device.
At the time the user desires to be authenticated, new biometric data 210 is collected, including data from the cartridge 211 , data regarding the alpha-numeric sequence 212 , and data from the motion sensors 213 . As an additional security measure, the comparison algorithm has an option to produce a unique real-time security code 217 to be used in the generation and encryption of test data. The security code 217 would be used only once. It is important to realize that the design of the pen 102 allows two-way communication between the pen and the data acquisition device. The complete set of test data 214 is then encrypted 215 using the same process as described above for the reference data to form an encrypted set of test data 216 . The encrypted test data 216 is compared to the encrypted reference data 206 . If the two data sets match, the user is authenticated 221 . If the two data sets do not match, the user is rejected 222 .
It is important to recognize that, after the reference sample is collected, the actual writing may be discarded because the reference sample itself is not matched with the test sample. If we were to simply store the reference signature and compare the test signature with the reference signature, one could easily copy the reference signature and match that signature when authentication is desired. However, in the present invention, the encrypted version of the reference signature, one that contains much more data than just the signature itself, is compared to the encrypted version of the test signature, again containing much more information than just the signature itself.
Because the reference data is an encrypted combination of a multiplicity of data, it serves no purpose other than as a verification key. Even if the server upon which the encrypted reference data resided was stolen, the thief would be unable to re-create a signature from the data because the encrypted reference data includes variables unknown to the thief. The thief would need to be able to recreate the phase, both speed and angle, at the time of the test data in order for the system to decrypt the lock. Simply recreating a perfect signature match with all the proper pen strokes will not suffice.
While the present system and method has been disclosed according to the preferred embodiment of the invention, those of ordinary skill in the art will understand that other embodiments have also been enabled. Such other embodiments shall fall within the scope and meaning of the appended claims. | This present invention includes a method for capturing and transmitting data captured from a writing instrument in a secure manner. More specifically, the biometric information collected from the pen is coupled with at least one additional data point for encryption. The user initially uses the pen to create a signature which is converted into an encrypted reference value in accordance with the present invention. When authentication is desired, the user uses the same or similar pen to create a signature which again is converted into an encrypted data value. Thereafter, the encrypted reference value is compared to the encrypted data value to determine if the values substantially match. There is not need to retain the original reference signature, thereby enhancing the security of the overall system. | 6 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates in general to operations in oil and gas wells, and in particular to completion operations with a ball launcher for successively launching an indefinite number balls into a wellbore while mounted on a wellhead assembly.
2. Description of Related Art
Balls are sometimes launched into a wellbore promote oil and gas flow from a hydrocarbon producing wellbore. Reasons for injecting the balls including using a ball as a sealing member by having the ball land on a seat formed on an end of a tubular, where the inner diameter of the tubular is less than the outer diameter of the ball. In other applications, balls may be forced with pressure through a tubular for cleaning the tubular (similar to a pigging operation) or otherwise removing debris or obstructions within the tubular. Balls may be mixed with a treating fluid that is injected into an adjoining formation that produces oil and gas. Additional examples include landing the ball in a segment of casing to divert a flow of cement during staging operations. Balls dropped within a wellbore are also used to activate tools downhole, such as by shearing a pin or directly contacting a switch or other device for activating a tool. From time to time the ball may be used to operate as a safety valve. Typically, as the wellbore is generally at a pressure greater than ambient pressure at the surface, the balls are held for a period of time within a pressurized environment prior to being dropped into the wellbore.
BRIEF SUMMARY OF THE INVENTION
Disclosed herein are example embodiments of a ball launcher for delivering balls into a wellbore. In an example embodiment a ball launcher includes a manifold body that has an axial bore in communication with the wellbore. A magazine is included that mounts on an end of the manifold body, where a cylinder is included with the magazine. A chamber extends axially through the cylinder; thus the cylinder can be rotated to align the chamber with the axial bore and a ball in the chamber can be launched into the axial bore for delivery to the wellbore. In an example embodiment, the ball launcher includes a launch system above the magazine. The launch system has a reciprocating launch rod for pushing the ball downward in the axial bore. In an example embodiment, the ball launcher includes a collet assembly and seal on a lower end of the rod for coupling with a profile in an outer circumference of the axial bore. In an example embodiment, the ball launcher includes an auxiliary line in the manifold body having an end in fluid communication with a flushing fluid and an end in fluid communication with the axial bore. In an example embodiment, the ball launcher includes a valve in the axial bore, so that when the valve is closed a pressure barrier is formed in the axial bore across the valve. In an example embodiment, the ball launcher includes another valve in the axial bore spaced axially away from the valve, so that when the another valve is closed a pressure barrier is formed in the axial bore across the another valve. In an example embodiment, the ball launcher includes a chamber with a ball disposed therein. In an example embodiment, wherein the end of the manifold body distal from the magazine is mounted on a wellhead assembly. In an example embodiment, the ball launcher includes notches on an outer periphery of the cylinder profiled for engagement by a ratcheting actuator for rotating the cylinder.
Also disclosed herein is an example of a wellhead assembly on a wellbore. In an example embodiment, the wellhead assembly includes a production tree mounted on a wellhead housing. A main bore projects through the production tree and wellhead housing and into communication with the wellbore. A manifold body is included on the production tree, where the body has an axial bore that is open to the main bore. A ball chamber is included that is in a cylinder, where the cylinder rotates into a position with the ball chamber offset from the axial bore and also rotates into a position with the ball chamber in registration with the axial bore. In an example embodiment, the wellhead assembly includes a rod insertable into the axial bore to form a pressure seal in the axial bore. In an example embodiment, the wellhead assembly includes valves spaced axially apart in the manifold body and selectively and independently closed to each form a pressure barrier across the axial bore. In an example embodiment, the wellhead assembly includes a flush line intersecting the axial bore between the valves for providing a flushing fluid to urge a ball down into the wellbore. In an example embodiment, the wellhead assembly includes a plurality of ball chambers formed through the cylinder along a circular path and oriented substantially parallel with the axial bore. In an example embodiment, the wellhead assembly includes a ratcheting device for selectively rotating the cylinder so the ball chambers register with the axial bore.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
Some of the features and benefits of the present invention having been stated, others will become apparent as the description proceeds when taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a side partial sectional view of an example embodiment of a ball launcher in accordance with the present invention.
FIGS. 2 and 3 are side partial sectional views of the ball launcher of FIG. 1 in an example of use.
FIG. 4 is a side partial sectional view of an example embodiment of a ball launcher in accordance with the present invention.
FIGS. 5 and 6 are side partial sectional views of the ball launcher of FIG. 4 in an example of use.
FIG. 7 is a plan view of a magazine portion of a ball launcher in accordance with the present invention.
While the invention will be described in connection with the preferred embodiments, it will be understood that it is not intended to limit the invention to that embodiment. On the contrary, it is intended to cover all alternatives, modifications, and equivalents, as may be included within the spirit and scope of the invention as defined by the appended claims.
DETAILED DESCRIPTION OF THE INVENTION
The apparatus and method of the present disclosure will now be described more fully hereinafter with reference to the accompanying drawings in which embodiments are shown. This subject of the present disclosure may, however, be embodied in many different forms and should not be construed as limited to the illustrated embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Like numbers refer to like elements throughout. For the convenience in referring to the accompanying figures, directional terms are used for reference and illustration only. For example, the directional terms such as “upper”, “lower”, “above”, “below”, and the like are being used to illustrate a relational location.
It is to be understood that the subject of the present disclosure is not limited to the exact details of construction, operation, exact materials, or embodiments shown and described, as modifications and equivalents will be apparent to one skilled in the art. In the drawings and specification, there have been disclosed illustrative embodiments of the subject disclosure and, although specific terms are employed, they are used in a generic and descriptive sense only and not for the purpose of limitation. Accordingly, the subject disclosure is therefore to be limited only by the scope of the appended claims.
Shown in partial side sectional view in FIG. 1 , is an example embodiment of a ball launcher 20 mounted on a wellhead assembly 22 . In the example of FIG. 1 , the ball launcher 20 includes a manifold body 24 having an axial bore 26 formed therethrough. The upper end of the wellhead assembly 22 includes a production tree 27 on which the manifold body 24 is mounted. A main bore 28 is shown axially formed in the production tree 27 and registering with the axial bore 26 and the manifold body 24 . The main bore 28 also extends downward and within a wellhead housing 29 , on which the production tree 27 mounts, and into communication with a wellbore 30 that projects into a formation 32 below the wellhead assembly 22 . The manifold body 24 of FIG. 1 further includes auxiliary lines 34 , 36 that intersect and project radially outward from the axial bore 26 . Wing valves 38 , 40 are set within the auxiliary lines 34 , 36 that selectively open and close to regulate flow through the auxiliary lines 34 , 36 . Passages 42 , 44 are also shown formed laterally through the manifold body 24 that intersect with the axial bore 26 . In the embodiment of FIG. 1 , the passages 42 , 44 are substantially parallel with auxiliary line 36 and disposed respectively above and below the auxiliary line 36 . Valve assemblies are provided within the passage 42 that is made up of a gate 46 mounted on an end of a valve stem 47 .
The gate 46 is shown extending within the axial bore 26 and when set in a closed position provides a pressure seal in the axial bore 26 . Similarly, a gate 48 with attached valve stem 49 is set within the passage 44 . The gate 48 also provides a pressure barrier within the axial bore 26 when set in its closed position. Actuators 50 , 52 are provided with each of the valve assemblies for selectively reciprocating the valve gates 46 , 48 and valve stems 47 , 49 within the passages 42 , 44 to set or remove a pressure seal within the axial bore 26 .
Further illustrated in the example embodiment of FIG. 1 is a generally planar magazine assembly 54 shown set on an upper end of the manifold body 24 and opposite where the manifold body 24 mounts to the production tree 27 . The magazine assembly 54 of FIG. 1 includes a planar base 56 that extends substantially over the upper end of the manifold body 24 and having a portion thereof that may optionally extend past the outer periphery of the manifold body 24 . Set on the upper surface of the base 56 is a cylinder 58 whose outer radial periphery extends at least from a lateral end of the base 56 and projects past where the base 56 is intersected by an axis A X of the axial bore 26 . The cylinder 58 of FIG. 1 has an axis A C that is laterally offset from and generally parallel with axis A X . The cylinder 58 has a diameter exceeding its thickness/height. The cylinder 58 is provided with chambers 60 1 - 60 n ( FIG. 7 ) that each define an open passage through the cylinder 58 and in a direction substantially parallel with the axis A X . Balls 62 1 - 62 i are shown set within each of the chambers 60 1 - 60 i ; each ball 62 1 - 62 i may have the same or a different shape and/or diameter than any other ball 62 1 - 62 i . Optionally, more than one ball 62 1 - 62 i may be provided within one or more of the chambers 60 1 - 60 i . The base 56 also includes an opening 64 that is formed therethrough and in a direction generally parallel with the axis A X . In the embodiment of FIG. 1 , the opening 64 registers with the axial bore 26 thereby allowing access to within a portion of the axial bore 26 through the magazine assembly 54 .
Shown in FIG. 2 , the ball 60 1 within the chamber 62 1 registered with the opening 64 in FIG. 1 is shown having fallen through the opening 64 and dropping within the axial bore 26 . Valve gate 46 has been retracted within the passage 42 by the actuator 50 to open the axial bore 26 and allow ball 62 1 travel downward past the passage 42 to the lower valve gate 48 . Referring now to FIG. 3 , valve gate 46 is reinserted into the axial bore 26 by the actuator 50 to reform the pressure seal in the axial bore 26 . Conversely, valve gate 48 is shown pulled from within the axial bore 26 and out of the path of the ball 62 1 so it can continue to travel downward into the production tree 27 . A swab valve 65 in the production tree 27 is selectively put into an open position so the ball 62 1 may enter the main bore 28 on its way downward into the wellbore 30 below.
An alternate embodiment of the ball launcher 20 A is provided in a side partial sectional view in FIG. 4 in which a launch system 66 is included. In the example embodiment of FIG. 4 , the launch system 66 mounts on an upper surface of the base 56 and includes an elongated support 68 having an end that bolts onto the base 56 . The support 68 extends generally axially away from the magazine assembly 54 and curves up to where it attaches to a launch assembly 70 ; which is shown suspended above the magazine assembly 54 on the support 68 . The launch assembly 70 reciprocates a launch rod 72 , which is shown extending partially within the launch assembly 70 . In one example embodiment, the launch assembly 70 may be hydraulically driven and include a piston 74 that attaches to the launch rod 72 and axially reciprocates within a cylindrical housing 76 . The end of the launch rod 72 facing the magazine assembly 54 includes a tip 78 and locking plug 80 depending from the lower end of the tip 78 . The locking plug 80 is provided with a shaped profile 82 on its outer periphery and configured for engagement with a profile 84 shown formed within the manifold body 24 along the outer circumference of the main bore 26 . The embodiment of the launch assembly 20 A of FIG. 4 is shown having a single valve gate 48 disposed in passage 44 . Also, an optional protective screen 86 is illustrated provided in the entrance to auxiliary line 36 from the axial bore 26 .
Referring now to FIG. 5 , launcher 20 A is shown in a configuration wherein the launch assembly 70 urges the launch rod 72 and launch rod tip 78 through the chamber 60 1 , through the opening 64 , and into the axial bore 26 . Urging the launch rod 72 a designated amount into the axial bore 26 allows engagement between the profiles 82 of the launch assembly 70 and the profiles 84 in the manifold body 24 . In an example embodiment, a pressure seal is formed within the axial bore 26 where the locking plug 80 with its profiles 82 engage the profiles 84 . The ball 62 1 is shown within the axial bore 26 and on the valve gate 48 , where either gravity or the launch rod 72 may urge the ball 62 downward into the axial bore 26 past the passage 42 and to rest on the gate 48 . In environments where the wellhead assembly 22 is subjected to freezing conditions, fluids in the axial bore 26 may thicken and/or freeze to impede travel of the ball 62 1 , thus the launch assembly 70 may be required to force the ball 62 1 downward past any such obstacles. As noted above, the passage 44 is set below the auxiliary lines 34 , 36 and at a distance so that the upper end of the ball 62 1 remains below the auxiliary lines 34 , 36 .
As illustrated in a partial side sectional view in FIG. 6 , the gate 48 is drawn into the passage 44 from the axial bore 26 thereby opening the axial bore 26 to communication in the space from the auxiliary lines 34 , 36 into the main bore 28 of the production tree 27 . As the engagement of the locking plug 80 with the axial bore 26 forms a pressure seal isolating the axial bore 26 from ambient, a flushing fluid may be introduced through one or both of the auxiliary lines 34 , 36 and into the axial bore 26 below the profiles 84 . The flow of the fluid, coupled with pressure in the fluid, can be used for urging the ball 62 1 downward past the lower end of the axial bore 26 , through swab valve 65 , and into the wellbore 30 .
A plan view of the magazine assembly 54 is provided in FIG. 7 . In this example it can be seen that the cylinder 58 is provided with a plurality of chambers 60 1-n shown formed in a generally circular path along the outer periphery of the cylinder 58 . In the example of FIG. 7 , each of the chambers 60 1-n is provided with a corresponding ball 62 1-n . Embodiments exist wherein one more chambers 60 1-n may be empty, or include more than one ball. Further provided in the example embodiment of FIG. 7 are notches 92 provided on the outer periphery of the cylinder 58 . In the example embodiment of FIG. 7 , the notches 92 have a generally triangular shaped outline and extend the entire height or thickness of the cylinder 58 . Alternate embodiments exist wherein the notches 92 have rectangular, and/or curved shapes, and may extend along only a portion of the thickness of the cylinder 58 . Optionally, profiled surfaces, such as depressions along an upper or lower surface may be provided on the cylinder 58 in lieu of the notches 92 .
Also shown set on the upper surface of the base 56 is a spring loaded pawl 94 having a tip profiled to engage the notches 92 and to limit rotation of the cylinder 58 to a single direction, i.e. clockwise or counterclockwise. Rotating the cylinder 58 can be accomplished by a ratcheting actuator 96 , also shown set on the base 56 and having an arm that reciprocates away from its body with a profile tip to engage the notches 92 thereby rotating the cylinder 58 . A spindle 98 may be included that is shown at approximately the center of the cylinder 58 that can extend into the base 56 thereby allowing rotation of the cylinder 58 with respect to the base 56 .
In an example of operation of the ball launcher 20 , a ball 62 1 or balls 62 1-n may be set within a chamber 60 1 or chambers 60 1-n and the cylinder 58 rotated by the actuator 96 so that a designated chamber 60 1 may be aligned with the opening 64 of the magazine assembly 54 so the ball 62 1 drops into the axial bore 26 . Moving the valve gates 46 , 48 , in conjunction with a flushing fluid provided through the auxiliary lines 34 , 36 , moves the ball 62 1 into the wellbore 30 . Optionally, one of the auxiliary lines 34 , 36 can be used to vent pressure from the axial bore 26 to allow the ball 62 1 to drop from the chamber 60 1 into the axial bore 26 . The actuator 96 may be reactivated to rotate the cylinder 58 thereby aligning another chamber 60 with the opening 64 and repeating the process for delivering additional balls 62 into the wellbore 30 . One or both of the auxiliary lines 34 , 36 may be used as a blow down line to relieve pressure trapped in the axial bore between the valve gates 46 , 48 . Thus prior to reopening valve gate 46 one or both of the wing valves 38 , 40 can be opening to vent pressure in the axial bore 26 .
An example use of the embodiment of FIGS. 4-6 , the ball 62 1 within the aligned chamber 60 1 may be urged into the axial bore 26 using the launch assembly 70 . After the launch rod 72 is drawn out of the axial bore 26 by the launch assembly 70 the magazine assembly 54 may be rotated as described above for alignment of another chamber 60 i for delivery of another ball 62 k .
An advantage of the device described herein is that an indefinite number of balls 62 can be delivered into the wellbore 30 merely by placing a ball 62 within any chamber 60 . It should be pointed out that continuous operation can occur without the need for removing the magazine assembly 54 from the rest of the ball launcher 20 .
While the invention has been shown or described in only some of its forms, it should be apparent to those skilled in the art that it is not so limited, but is susceptible to various changes without departing from the scope of the invention. | A ball launcher for dispatching balls into a wellbore that includes a manifold for selective attachment to a wellhead assembly and a magazine mounted on the manifold in which the balls are stored for distribution to the manifold. Chambers are provided in a cylinder in the magazine, so that by rotating the cylinder the chambers register with a bore in the manifold, through which the balls are delivered to the wellbore. Flowing a flushing fluid into the bore in the manifold urges the balls downward. An auxiliary line through the manifold provides a conduit for the flushing fluid into the bore. | 4 |
RELATED APPLICATIONS
This application is a continuation-in-part of Provisional application Ser. No. 60/008,690 filed Dec. 15, 1995; and a continuation-in-part of application Ser. No. 08/338,346 filed Nov. 14, 1994, now U.S. Pat. No 5,688,014.
FIELD OF THE INVENTION
The invention pertains to power-operated toggle clamps and grippers.
BACKGROUND OF THE INVENTION
Conventional toggle clamps comprise at least one clamping arm that is pivotally connected through links to a base support. It is well known that, as the links toggle, a point is reached and passed at which the compressive and tension stresses in the links and clamp arm are theoretically infinitely large.
The internal stress in the links and the clamping arm is relieved to some extent by their inherent (albeit slight) elasticity, which can save the parts from fracturing. Still, one undesirable consequence of the great unpredictable internal stress occurring at the toggle point is that the pins connecting the links and the pin on which the clamp arm swings are subject to a powerful shearing force. Since there is no motion between the pivot points and the links at the toggle point, the high shearing or bearing stress causes rapid wear of the pins and/or in the links, which are journaled on the pins. If the size of the article being clamped varies by as little as 0.015 inch (0.38 mm) the clamping force can vary by 25%-50%.
If the article size exceeds specifications, internal stress of the clamp parts is even greater. If the article size is under specification, the article may slip in the clamp which can result in damage to property or injury to a person in an industrial setting.
Furthermore, clamps or grippers without mechanical locking can release parts during a pressure loss or pressure drop. The failure at an unclamped condition can occur when pressure decreases after locking. When the pressure decreases, the cylinder has less available force to open. This problem is aggravated by mechanisms designed to clamp on the advance stroke of the cylinder.
A number of clamp manufacturers have moved to so-called "Wedge Locking" designs in order to avoid the toggle unlocking problem. Wedge Locking clamps are designed to stop before reaching a locked position and therefore are not true locking mechanisms. Under severe vibration, wedge clamps can lose mechanical locking.
Furthermore, current enclosed clamp designs have a cantilevered shaft protruding from the side of the clamp where the arm is attached. This type of loading causes bending, torsion, and shear loading, severely reducing the load capacity of the clamp.
These shortcomings, taken alone or in combination, call for improved clamping and gripping devices.
SUMMARY OF THE INVENTION
One aspect of the invention provides a toggle clamp whose operating characteristics can be easily changed. The clamp comprises a frame having an exterior. A first pin having an axis is supported by the frame for movement transverse of the axis. A second pin having an axis parallel to the axis of the first pin is supported by the frame against movement. An arm is carried by the first pin for rotation about the axis of the first pin in a first direction applying pressure to a load and a second direction releasing the pressure. The clamp includes a spring element on the exterior of the frame, which is coupled between the first and second pins. The spring element exerts a spring force that biases the first pin toward the second pin. The spring element maintains symmetric loading on the two pins. The spring element, being accessible on the exterior of the frame, can be readily released and exchanged with another spring element to change the spring force.
Another aspect of the invention provides a toggle clamp having improved performance during partial or total actuator failure. The clamp is adapted for connection to an actuator of the type that applies force in an advance stroke and in a retract stroke. The clamp comprises a movable first pin and a stationary second pin. A spring element is coupled between the first and second pins and exerts a spring force that biases the movable first pin toward the stationary second pin. An arm is carried by the first pin for rotation in a first direction applying pressure to a load and a second direction releasing the pressure from the load. The clamp includes linkage coupled to the arm. The linkage is adapted and arranged for connection to the actuator to rotate the arm in the first direction, applying pressure to the load, during the retract stroke and to rotate the arm in the second direction, releasing pressure from the load, during the advance stroke.
In the event of total actuator failure, the spring element maintains the arm in a condition applying pressure to the load. Still, the spring force can be selected to permit the operator to manually return the arm to a condition releasing pressure from the load. In the case of partial failure of the actuator, the linkage returns the arm to the pressure release condition during the advance stroke, thus making available greater force to unlock the clamp.
In a preferred embodiment, the clamp is totally enclosed to assure reliable operation possible under harsh conditions.
Other features and advantages of the invention will be pointed out in, or will be apparent from, the drawings, specification and claims that follow.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view of the exterior of a gripping device that embodies features of the invention;
FIG. 2 is a top view of the exterior of the gripping device shown in FIG. 1;
FIG. 3 is an end sectional view of the device shown in FIG. 1, taken generally along line 3--3 in FIG. 1;
FIG. 4 is a side view of the interior of the gripping device shown in FIG. 1, with the gripping arms located in their clamping position;
FIG. 5 is a side view of the interior of the gripping device shown in FIG. 1, with the gripping arms located in their unclamping position; and
FIG. 6 is a side view of the device shown in FIG. 1 configured as a clamping device.
The invention is not limited to the details of the construction and the arrangements of parts set forth in the following description or shown in the drawings. The invention can be practiced in other embodiments and in various other ways. The terminology and phrases are used for description and should not be regarded as limiting.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIGS. 1 to 3 show a clamping device 10 attached to a base 12 and coupled to a hydraulic or pneumatic actuator 14. As best shown in FIGS. 2 and 3, the clamping device 10 includes a right side casting body 16 and a left side casting body 18 aligned and joined by bolts 20.
A top main pivot pin 22 passes through opposing holes in the casting bodies 16 and 18, secured by retaining rings 26. The top main pivot pin 22 carries a top gripping arm 28. The top gripping arm 28 rotates about the top main pivot pin 22.
As FIG. 3 best shows, the holes 24 through which the top main pivot pin 22 passes are enlarged beyond the outside diameter of the pivot pin 22. Movement of the top main pivot pin 22 within the holes 24 is thereby allowed.
A bottom main pivot pin 30 passes through opposing holes 32 in the casting bodies 16 and 18, also secured by retaining rings 26. The bottom main pivot pin 30 carries a bottom gripping arm 34. The bottom gripping arm 34 rotates about the bottom main pivot pin 30.
As FIG. 3 best shows, the holes 32 through which the bottom main pivot pin 30 passes are not elongated beyond the outside diameter of the bottom main pivot pin 30. Thus, substantially no movement of the bottom main pivot pin 30 is allowed. The bottom main pivot pin 30 is essentially stationary.
Springs 36 are coupled between the top and bottom main pivot pins 22 and 30 at both ends of the pivots pins 22 and 30, which are exposed for access from the exterior of the casting bodies 16 and 18. The springs 36 normally bias the top main pivot pin 22 toward the bottom main pivot pin 30. The bias of the springs 36 normally leaves a gap 38 (see FIG. 3) within the oversized holes 24 through which the top main pivot pin 22 passes. As FIG. 3 shows, the spring normally biases the top main pivot pin 22 so that the gap 38 exists above the pin 22. The top main pivot pin 22 is thereby allowed to float within the gap 38, subject to the spring bias.
As FIGS. 3 and 4 show, an interior groove 40 is formed in the mating casting bodies 16 and 18. The groove 40 has an axis 42 (see FIG. 4), which extends transverse to the parallel axes 44 of the top and bottom main pivot pins 22 and 30.
As FIGS. 4 and 5 show, a slider 46 is coupled to the actuator 14 for lateral movement within the groove 40. The actuator is of a conventional type that has an advance stroke and a retract stroke.
Advancement of the actuator (arrow 48 in FIG. 5) moves the slider 46 in a forward direction, toward the gripping arms 28 and 34. Retraction of the actuator (arrow 50 in FIG. 4) moves the slider 46 in a rearward direction, away from the gripping arms 28 and 34.
The slider 46 carries a pivot pin 52. A pair of upper links 54 are attached at opposite ends of the slider pivot pin 52 (see FIGS. 3 to 5). The opposite ends of the upper links 54 are commonly attached to an upper link pivot pin 56 carried by the top gripping arm 28. The upper link pivot pin 56 is located rearwardly of and is axially displaced from the top main pivot pin 22.
A pair of lower links 58 are attached at one end to the slider pivot pin 52, radially inboard of the upper links 54 (see FIG. 3). The opposite ends of the lower links 58 are commonly attached to a lower link pivot pin 60 carried by the bottom gripping arm 34. The lower link pivot pin 60 is located rearwardly of and is axially displaced from the bottom main pivot pin 30. The axes 62 of the upper and lower link pivot pins 56 and 60 are mutually aligned in a spaced apart and parallel relationship.
The upper and lower links 54 and 58 translate linear movement of the slider 46 into synchronized rotational movement of the gripping arms 28 and 34. When the slider 46 is in its rearward most position (as FIG. 4 shows), the gripping arms 28 and 34 are mutually disposed in a clamping position. As the actuator advances (arrow 48 in FIG. 5), movement of the slider 46 in the forward direction pivots the upper and lower links 54 and 58 in synchrony about the slider pivot pin 52 and about the upper and lower link pivot pins 56 and 60. The gripping arms 28 and 34 pivot in synchrony about the top and bottom main pivot pins 22 and 30 away from each other, from the clamping position to an unclamping position (shown in FIG. 5). As FIG. 5 shows, the gripping arms 28 and 34 open a full ninety degrees when in the unclamping position for maximum tooling clearance.
Likewise, as the actuator retracts (arrow 50 in FIG. 4), movement of the slider 46 in the rearward direction pivots the links 54 and 58 in synchrony about the slider pivot pin 52 and about the upper and lower link pivot pins 56 and 60, to pivot the gripping arms 28 and 34 about the top and bottom main pivot pins 22 and 30 from the unclamping position to the clamping position (shown in FIG. 4).
As the gripping arms 28 and 34 move from the unclamping position toward the clamping position (i.e., as the actuator retracts), the links 54 and 58 toggle as they pass through vertical. Once beyond vertical in the forward direction, the links 54 and 58 mechanically lock the gripping arms 28 and 34 in the clamping position.
With conventional actuators, actuator advancement will typically provide greater force than actuator retraction, because there is generally less pressure area on the retraction side of an actuator stroke. By virtue of the above described construction, the gripping arms 28 and 34 are movable to the unclamping position (FIG. 5) during advancement of the actuator 14 (arrow 48 in FIG. 5). Thus, should the actuator 14 fail partially, thereby decreasing the overall available actuation force, the device 10 nevertheless provides greater application of remaining force by employing an advancement stroke to release a load.
Should the actuator 14 fail completely when the gripping arms 28 and 34 are in their clamping position, the bias of the springs 36 will maintain the toggled, mechanically locked condition of the links 54 and 58. Still, in the absence of actuator force to release the load, the operator need only overcome the biasing force of the springs 36 to move the gripping arms 28 and 34 to their unclamping position, thereby releasing the load.
By virtue of the above described construction, loads applied to the top gripping arm 28 are transmitted through the top main pivot pin 22 to both springs 36. As the springs 36 deflect, the top main pivot pin 22 will float in the gap 38. The springs 36 thereby serve to distribute the load evenly along the axes 44 of both top and bottom main pivot pins 22 and 30. Symmetrical loading through the center of the top and bottom main pivot pins 22 and 30 reduces the chance of failure caused by unequal load distribution.
In the illustrated and preferred embodiment (see FIG. 2), the springs 36 are accessible from the exterior of the device 10. This accessibility permits easy repair and replacement of springs 36. The operating characteristics of the device 10 can therefore be readily adjusted by interchanging springs 36 having different spring constants. The springs 36 shown in the preferred embodiment are C-shaped, or curved beam types. Values for load, deflection, and stress for curved beam types are known and readily available.
For example, the spring constant values can be varied, by interchanging springs 36, to regulate stress to control loads and deflections. As another example, the spring constant values can be varied, by interchanging springs 36, to regulate load pressure and to regulate load release force, should actuator failure occur. A constant load can be achieved using springs 36 with a constant load output. As another example, the spring constant values can be varied, by interchanging springs 36, to change the gripping range (gripping range is the ability of the clamp or gripper to hold parts that vary (substantially) in size). Gripping range can be increased by selecting springs 36 having greater deflection. Changes in part tolerance as small as 0.010 inch can cause clamping forces to increase or decrease as much as 50%. This can result in an unclamped condition producing scrap parts, broken tools, or personal injury. The device 10 makes possible the quick interchange of springs 36 to adjust to changing load demands.
Furthermore, greater strength and manufacturing economy are gained by placing the springs 36 in the location shown in the drawings, instead of on a gripping arm 28 or 34. If the spring is placed at the end of the gripping arm, the distance between the gripping arm and the part being gripped must increase to accommodate the spring. Any other location of the spring on the gripping arm may require decreasing the strength of the arm.
As best shown in FIGS. 4 and 5, the device 10 is fully enclosed. The two radii R1 and R2 of the gripping arms 28 and 34 (see FIG. 4) maintain close contact with the casting bodies 16 and 18 during arm rotation. Close tolerances between the gripping arms 28 and 24 and the casting bodies 16 and 18 are thereby maintained. The close tolerances lead to small openings, which keep debris from entering the interior of the device 10. A totally enclosed design allows the device to operate in harsh conditions. This is especially important in welding conditions, where weld spatter can jam the clamp or gripper mechanism.
Seals could be placed at the openings, to further eliminate even the smallest particles from entering the mechanism, but in most cases the extremely small opening should be enough to filter debris.
As FIG. 6 demonstrates, the device 10 is capable of operating as a clamp, using a single gripping arm 28. If a single gripping arm 28 is used, the springs 36 are still anchored between the top and bottom main pivot pins 22 and 30 in the manner shown in FIG. 1. As FIG. 6 shows, a plate 64 is provided to close the area 66 where the gripping arm 34 is removed.
Features and advantages of the invention are set forth in the following claims. | A toggle clamp includes a movable first pin having an axis and a stationary second pin. An arm is carried by the first pin for rotation in a first direction applying pressure to a load and a second direction releasing the pressure. An exterior spring element is coupled between the first and second pins. The spring element exerts a spring force that biases the first pin toward the second pin. The spring element is releasable for exchange with another spring element to change the spring force. | 1 |
BACKGROUND OF THE INVENTION
This invention relates to raised pavement markers that utilize a plurality of light reflecting prisms each with three intersecting surfaces.
This type of raised marker have been used extensively, especially the types with the reflective cube corner elements.
Roadmarkers are mounted on the pavement along the edgeline, centerline or as lane dividers. Markers of this type are usually made of either one-piece or two-piece housing, made of compatible thermoplastic materials with at least one metalized reflective face. Prior to filling the entire housing with a plastic material for rigidity and strength, the reflective portion of the housing are coated with a metalized layer to retain part of its retro-reflective ability. This metalization process, although retaining part of the retro-reflective ability of the three intersected surfaces of the prisms, it also retards portions of the light reflecting out of the three surfaces of the reflecting prisms.
Experience has also proven that the smooth exterior surfaces of the reflecting faces of the markers oriented at an acute angle with the road surface tend to reduce its reflective ability shortly after usage, due to the action of dirt with tire passage.
Among the objectives of this invention are to offer a pavement marker which has an enhanced reflectivity, abrasing reducing raised element which is integrally part of the housing; enlarged reflective faces; and, low cost. Furthermore, this invention enhances the outside angular configuration of the pavement marker to reduce the protrusion from the roadway, thereby reducing impact shocks to the passing vehicles.
SUMMARY
The primary objective of this invention is to provide an improved pavement marker of the type consist of one piece shell formed with reflective faces, the reflective faces metalized and entire shell filled with organic material for strength. This has been achieved by developing integrally molded housing, having one or two opposing faces with light reflecting elements, each reflective face is integrally divided into rhombic shaped cells. Each cell contains a planar surface on the outside to intercept light from oncoming vehicles and either a single reflective element or plurality of reflective elements within the inside surface of each rhombic shaped cell. The rhombic shaped cells are isolated from each other by slightly raised members on the outside surface and by a corresponding partition walls from the inside surface. A backing sheet adhered onto said partition walls, seal and isolate each cell, freeing the three surfaces of the reflecting elements within each cell from encapsulation by the filler material. Hence, the reflectivity achieved without vacuum metalizing the reflecting elements.
Another objective of this invention is to provide an improved pavement marker of the type using load carrying partition walls. This has been achieved by incorporating on the outside surface of the reflective face slightly raised members and nearly directly above the partition walls, thereby freeing the reflective cells from direct impact and permitting light impinging on the outside surface of the reflective cells to bounce back freely toward the vehicle line of sight.
Another objective of this invention is to provide an improved reflective highway marker utilizing multi-angled sides of relatively simple design, yet protrude a slight amount from the roadway surface, thereby reducing the vehicles' impact upon tire contact with said marker.
Still another objective of the present invention is the enhanced area of the reflective faces which can provide greater area of reflectivity than presently is achieved.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a plan view of one embodiment of the pavement marker of this invention.
FIG. 2 is an elevation view of the pavement marker of FIG. 1
FIG. 3 is a section through Line 1--1 on FIG. 1.
FIG. 4A is a plan view of a preferred form of a rhombic shaped cell housing plurality of cube corner array, within the cell's partition walls.
FIG. 4B is another form of a rhombic shaped cell housing the cube corner elements within the partition walls.
FIG. 4C is a third form of a rhombic shaped cell housing a single cube corner reflector within the partition walls.
FIG. 5 is an enlarged portion of a segment of the reflective face that may be used in FIG. 1, showing relation between the incident light and the reflected light through free standing reflected element.
FIG. 6 is the same enlarged portion in FIG. 5 showing the relation between incident light and reflected light through metal coated reflective elements.
FIG. 7 is a fragmentary section view along the line 2--2 of FIG. 1.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Greatly enhanced reflectivity and durability for pavement markers can be achieved by the elimination of the process of metalizing the reflective elements of the present pavement markers and by incorporating raised members on the outside of the reflective faces to reduce direct contact, thereby reducing abrasing to the outside planar faces of said pavement marker.
This invention satisfies the above conditions.
Referring to the illustrated drawings of this invention, FIGS. 1 through 4C represent a pavement marker generally designated by the number 20, and comprises a housing 10, a backing sheet 50 and a rigid core 60. Part of the housing 10 is the planar face 11, having an outside surface with abrasing reducing and load transferring members 12 defining the planar surfaces 13 of the rhombic shaped cells, adopted to intercept light.
The inside surface of face 11 is divided into rhombic shaped cells 14, corresponding to planar surfaces 13 on the outside of face 11.
Each cell 14 incorporates either a singular or plurality of reflective elements 16. Cells 14 isolated from each other by partition and load carrying walls 15. The reflective elements 16 comprise cube corner reflective prisms. Each of the reflective surfaces of an element 16 positioned with respect to the wall 15 in such a particular manner to allow maximum reflectivity of the three reflective surfaces. The axis for each cube corner element form an acute angle i with the normal to the outside surface of the reflective face as in FIG. 3.
The housing 10 has side walls 30, each with two segments 31 and 32. FIG. 2 shows each of the segments 31 and 32 to be inclined with distinct angles A 1 and A 2 with respect to the vertical. Angle A 1 preferably within the range of about 5° to 15° and angle A 2 is within the range of about 15° to about 60°.
Due to this angular configuration of side 30, the tire impact force F in FIG. 2 will be reduced. This will be accomplished especiallly when the tire impact force F in FIG. 2 is due to traffic lane changes, which is the most frequent vehicular contact to pavement markers. This impact reduction primarily is due to the much lower contact height (H 1 ) instead of height (H 2 ) in FIG. 2.
The housing 10 of the pavement marker 20 may be fabricated from any suitable light-transmitting, impact and weather resistant material. The desired color can be achieved by pigmenting either all or part of the housing 10.
When desired, the pavement marker of FIG. 1 can be bi-directionally reflective by making the opposite face 40 optically equivalent to the reflective face 11.
FIG. 3 illustrates a sectional view showing a preferred construction of the pavement marker 20, the outer one-piece housing 10 which is made of a light transmitting organic resinous material. The entire inside portion of the reflective face 11 is sealed with a planar backing sheet 50, made of organic resinous material, then the entire housing 10 is filled with a rigid or resilient material to form core 60.
By using a thermosetting material like Epoxy to fill the core 60, it will provide a rugged structure that adheres well to the interior of housing 10 and the inside of backing sheet 50. Also the present marker will withstand vehicular impact on the roadway.
Since the reflective faces 11 and 40 can be identical in fabrication, we will describe face 11 only in detail.
The inside surface of reflective face 11 in FIG. 3 is integrally divided into plurality of rhombic shaped cells 14 by the partition walls 15 that extend beyond the tips or raised corners of all of the three mutually intersecting surfaces of the reflective elements 16 within each cell, thereby freeing all of the reflective elements from contact with the backing sheet 50. This creates an air space 70 between the reflective elements within each cell and the backing sheet 50, thereby allowing total reflection within the three intersecting surfaces of each reflective elements 16 without the need to metalize these reflective surfaces prior to filling housing 10 with a rigid material. FIG. 4A 4B and 4C show the preferred forms of the rhombic shaped cell 14 within inside surfaces of the reflective face 11 of housing 10. The size and number of the cube corner element 16 in a given rhombic cell is determined by the particular application of the marker and by the size of the load carrying partition walls used.
A brief background into how a non-metalized reflective cube corner elements or other reflective prisms would reflect light more effectively when they are freely functioning in an air medium (rare medium), instead of being coated with a metal layer.
FIG. 5 shows the relation between the so-called Poynting vectors L and L' where the vector L represents an incident of light from an oncoming vehicle and L' represents the incident of light traveling through the dense medium 35 of the face 11 that is made of a light transmitting organic resinous material having a predetermined reflective index n=1.5.
Hence, in our case: n=1.5=sin d/sin r Where d is the angle that the incident of light ray L forms with the normal line N to the outside surface of face 11 of the housing 10, and r is the angle that deflected light vector L' forms with the same normal line N within the dense medium 35 of face 11 of housing 10.
The mathematical relationship of vectors L, L', angles d and r and the reflective index n has been fully described in the text book (Introduction to Modern Optic, by Grant R. Fowles, published by Holt, Rinehart and Winston, Inc., 1968, pp. 47-58).
The author proved that vector L' as in FIG. 5 bounce back at the surfaces 74 and 75 which forms the boundary limits of the light transmitting dense medium 35, just as it reaches rare medium 70. This means that nearly total internal reflection takes place within the inner boundaries 74 and 75 of each reflective element 16 within a cell 14, that is light L' will turn around and bounce back within the dense medium 35. This is known as internal reflection.
FIG. 6 shows that when using the same reflective elements 16 with coated metal backing 71, the incident of light traveling through the light transmitting medium 35 of face 11 as it reaches the outer boundary 74 of the reflective elements 16, partly will be reflected onto the adjacent surface 75 and partly be absorbed by the metal coated surface 71, as indicated by the vectors T, K and T', K'. This is due to the face that the coated metal layer 71, which is usually aluminum, is a more dense medium than the light transmitting reflective elements that are part of the housing medium 35.
Therefore, it has been proven that light vector L'=L"' is greater than (K'). Where K' represents the ray of light bouncing back towards its origin, after partly being absorbed by the metalized surface 71 in FIG. 6 and L"' represents ray of light in FIG. 5, fully reflected on the surfaces 74 and 75 due to the uncoated free standing rare medium 70 behind it.
The above author indicates, however, that there is a critical value for the angle g in FIG. 5. In order to achieve total internal reflection of the incident of light passing through the free standing surfaces of the reflective elements 16, within a cell 14, the angle g has to be greater than the critical angle for the respective material used to fabricate the reflective face 11.
Another primary function of partition walls 15 and the corresponding raised member 12 which are integrally part of face 11 is to function as load carrying walls. The rhombic shaped configuration of these walls form a truss like rigid structure that act uniformly, transfer impact load evenly to the core and free reflective cell 14 from direct impact load.
In FIG. 7 the distributed load P acting on face 11, due to vehicular tire impact will be first acting on the abrasing reducing members 12 which are part of the outside surface of face 11. These raised elements 12 will be nearly directly above the corresponding partition walls 15 on the inside surface of face 11, thereby transferring the bulk of impact load P to the core 60 via the aglotinated backing sheet 50.
Another advantage of incorporating the rhombic shaped abrasing reducing elements 12 is to allow a reduction of angle (X) that face 11 forms with the horizontal (as shown in FIG. 3) without increasing the vehicular tire contact with face 11. Therefore, we can reduce the angle (X) thereby enlarging the reflective face 11. The angle (X) preferred to be from about 20° to about 50°. | A retro-reflective roadway marker is generally comprised of a one-piece housing, having integrally molded retro-reflective faces.
The reflective faces having outside surfaces with abrasing reducing raised members and inside surfaces of light reflecting elements that are preferably formed from three mutually intersecting surfaces.
In one form the reflective elements within the housing are integrally molded with partition walls, dividing the reflective elements into small cells, each cell with a plurality of the reflective elements functioning independently without being encapsulated by the filler material. | 4 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a United States National Phase application of International Application PCT/EP2010/000180 and claims the benefit of priority under 35 U.S.C. §119 of German Patent Application DE 10 2009 004 066.8 filed Jan. 6, 2009, the entire contents of which are incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The invention relates to pertains to a barrier layer arrangement for tank systems and more particularly to a barrier layer arrangement with gas-tight properties for containers for transporting and storing liquefied gases.
BACKGROUND OF THE INVENTION
[0003] Various types of tank systems are available for the transportation and storage of ultra cold liquids, for example, liquefied natural gas (LNG). Non-self-supporting membrane tanks, in which the containment system is installed directly on the load-bearing structure, represent a variant that is widely used because of the large cargo volume.
[0004] Membrane tank systems are made, corresponding to applicable sets of rules, e.g., the IGC Code, of at least one gas-tight barrier layer and at least one insulating layer; two gas-tight barrier layers are required in the example of the IGC code.
[0005] Shrinkage of the barrier material occurs due to the very low temperatures of the cargo being transported, which are, for example, −160° C. and lower. Since the tank system is rigidly connected to the load-bearing structure, these shrinkages are to be compensated by compensating elements.
[0006] Membrane tank systems being used currently use metallic materials as a barrier material and compensate the shrinkages by introducing compensators in the form of beads. The use of special alloys, for example, FeNi36, whose coefficient of thermal expansion is very low, is also known for minimizing shrinkages.
[0007] Based on the isotropic material characteristics (materials geometrically uniformly expanding or contracting during temperature changes), compensating beads are necessary in a plurality of directions, which inevitably causes beads to geometrically intersect each other. This requires crossing elements of complex shapes or the interruption of a bead, which leads to stress peaks in the barrier.
[0008] A multilayer panel for lining liquefied-gas containers with an insulating plate consisting of a heat-insulating material and a seal coating, in which the seal coating has a thermal compensator designed as an endless, e.g., circular bead, is known from WO 2008/125248.
SUMMARY OF THE INVENTION
[0009] An object arises to develop a barrier layer arrangement for tank systems, which has a simplified design and makes possible an automated, continuous manufacturing process, wherein the stresses occurring due to temperature changes shall be kept low.
[0010] A barrier layer arrangement for membrane tank systems with at least one layer is provided, wherein said layer is manufactured from a material with anisotropic properties. The anisotropic properties can be set in respect to the thermal expansion characteristics and preferably also in respect to the elasticity properties such that a value of a quotient of coefficients of thermal expansion in a secondary direction and coefficients of thermal expansion in a primary direction orthogonal to the secondary direction as well as preferably a value of a quotient of a modulus of elasticity in the primary direction and a modulus of elasticity in a secondary direction are each greater than 1.3.
[0011] The quotient of the coefficients of thermal expansion is especially preferably greater than 4 or greater than 20 and the quotient of the moduli of elasticity is greater than 2.
[0012] The material is preferably a composite. Due to the anisotropy of the coefficient of thermal expansion and of the modulus of elasticity, expansions and shrinkages caused by great temperature changes can be set specifically in a direction-dependent manner, and compensators may be introduced in one direction only.
[0013] The anisotropic properties of the composite, which may be designed as a fiber composite, can be defined by a design of a plurality of layers of a fiber material with oriented fibers, which said layers are arranged at certain angles in relation to one another, wherein, for example, three layers arranged at different angles in relation to one another are provided, and the angles of the layers in relation to one another are between −45° and 45° in relation to a defined primary direction. Angles between principal fiber directions of the layers shall be called angles between layers here. This design proved to be especially advantageous in previous experiments for bringing about anisotropic properties, and adjustment of the preset conditions, for example, by selecting the angles of the layers, is possible.
[0014] A membrane tank system can be defined as non-self-supporting tanks, which have walls consisting of a thin layer. The flexible walls may be supported via an insulating layer by surrounding structures of the ship. In addition, membrane tanks are usually designed exclusively for low overpressures of less than 0.7 bar or even less than 0.25 bar relative to an ambient pressure, as a result of which they can be manufactured in a substantially more material-saving manner than can pressurized gas containers.
[0015] In an advantageous embodiment, the angles of the layers arranged in relation to one another with reference to a defined primary direction may have the values 0°, 33° and −33° or the values 0°, 45° and −45°. The layered structure shows especially favorable properties for these values.
[0016] By using fibers with very low or negative coefficients of thermal expansion, such as carbon, polyethylene, PBO, aramid or glass fibers, it is possible to adjust the coefficient of thermal expansion of the barrier layer arrangement in the primary direction to a very low to negative value. Furthermore, it is possible, owing to the layered structure, to adjust the stiffness of the barrier layer arrangement in the secondary direction to a low value. As a result, hindered temperature-related shrinkages lead to low stresses.
[0017] The plurality of layers for designing an anisotropic composite may be formed exclusively from one type of fiber, for example, exclusively from carbon fibers or exclusively from glass fibers. In a hybrid design, at least two layers may be formed from different fiber materials. For example, one layer for designing an anisotropic fiber composite may be formed from carbon fibers and at least one layer from glass fibers. Since carbon fibers have a negative coefficient of thermal expansion, favorable properties are obtained for an anisotropic fiber composite especially when combined with layers from glass fibers.
[0018] The plurality of layers are advantageously arranged symmetrically with the central plane of the composite layer. The development of internal stresses is prevented hereby.
[0019] The layers may be designed as prepregs, consisting of endless fibers, which may also be in the form of a fabric, in a yet uncured plastic matrix, the matrix being manufactured from epoxy resin, polyester resin, polyurethane or another suitable material. Prepregs lead to a uniform and high quality, and low undulation (fiber deflection) and a high percentage of fibers is also advantageous. In addition, prepregs are well suited for machining and automated manufacturing processes.
[0020] The material parameters coefficient of thermal expansion and modulus of elasticity can be specifically adjusted by selecting the reinforcing material, filler, material for the matrix and layered structure. The coefficient of thermal expansion can be adjusted to a low value in the primary direction and the modulus of elasticity can be adjusted to a low value by the layered structure in a secondary direction, which is arranged at an angle of 90° relative to the primary direction. In particular, the coefficient of thermal expansion and the modulus of elasticity are relevant for the stresses and expansions occurring in a barrier at very low temperatures and can be adjusted specifically in a direction-dependent manner in a fiber-reinforced plastic.
[0021] Due to these properties, the barrier layer arrangement shrinks nearly exclusively in the secondary direction, which makes it possible to reduce the number of expansion compensators, and it may also become possible to use expansion compensators exclusively in one direction.
[0022] The barrier layer arrangement may be designed such that the at least one layer, which is made of a material having anisotropic properties, is gas-tight, especially such that the material having anisotropic properties is itself gas-tight.
[0023] Gas-tightness of the barrier layer arrangement may also be established by the anisotropic composite layer being connected to a gas-tight layer or to a liner, wherein the liner is manufactured, for example, from aluminum or polyethylene. Gas-tightness of the anisotropic composite layer itself is not absolutely necessary in this case.
[0024] In one embodiment, the at least one layer has beads in one direction only, for example, in the secondary direction, and the beads may be formed especially predominantly or exclusively for compensation of thermal expansions in one direction.
[0025] Even though beads are arranged in both directions in other embodiments, the total number of beads is smaller in a first direction and especially only half the total number of beads present in a second direction orthogonal to the first direction.
[0026] The beads may be designed, for example, as straight beads, but other shapes may be advantageous as well.
[0027] The anisotropic composite layer has a ratio of the coefficient of thermal expansion in the secondary direction to that in the primary direction of greater than 2 and, in the case of negative coefficients of thermal expansion, a value lower than −9, said ratio being dependent on the angles of the layers and the material of the fibers and of the matrix, as well as a ratio of the modulus of elasticity in the primary direction to that in the secondary direction of between 1.5 and 15.
[0028] The ratio of the coefficient of thermal expansion in the secondary direction to that in the primary direction may be greater than 3 or greater than 5 in alternative embodiments. In addition, the ratio of the modulus of elasticity in the primary direction to that in the secondary direction may be especially greater than 2 or 3.
[0029] The barrier according to the present invention, comprising at least one anisotropic composite layer, makes it possible, thanks to the low coefficient of thermal expansion, to reduce the number of compensators in the primary direction or to eliminate the need for compensators in the primary direction, which results in a marked simplification of the system.
[0030] The anisotropic composite layer can be manufactured in an automated, continuously operating manufacturing process with high quality in a time- and cost-saving manner.
[0031] The material having anisotropic properties is designed in some embodiments as a compact material, i.e., without inclusions of gases and/or liquids. Especially thin membranes can be prepared due to such a design. In addition, the anisotropic properties of compact materials can be better adjusted than those of foamed materials, because additional manufacturing irregularities occur in foamed materials due to the fact that the size of the cavities contained in the foamed material is variable at least to a certain extent.
[0032] In further embodiments, the anisotropic material contains additional materials or fillers and additives for modifying properties. For example, flame-retardant additives or pigments may be added.
[0033] In another embodiment, the value of the coefficient of thermal expansion of the anisotropic material is lower than 10-5/K, advantageously lower than 8×10-6/K and especially advantageously lower than 4×10-6/K in a direction in which the value of the coefficient of thermal expansion is minimal.
[0034] By minimizing or eliminating the compensator cross-related coupling of two directions of the system, it is possible to adapt the tank system to the site of use in a more variable manner.
[0035] The simplified construction is suitable for general use in ultra cold facilities such as transport and storage containers, e.g., tank containers, liquefied gas tanks onboard ships and offshore facilities as well as for land tanks. The containers may have various shapes, e.g., prismatic, cylindrical or spherical shapes or be composed of a plurality of shapes.
[0036] In addition to the barrier layer arrangement, the present invention also pertains to a membrane tank system for receiving ultra cold liquids, with an insulating layer and with a barrier layer arrangement of the type described.
[0037] In one embodiment each, the membrane tank system has a volume of at least 1,000 m3, 10,000 m3 or 50,000 m3.
[0038] In another embodiment, the membrane tank system can be loaded to a maximum of 0.7 bar or even only up to 0.25 bar overpressure and is not therefore designed for storing pressurized gas.
[0039] An exemplary embodiment of the present invention is shown in drawings and will be explained in more detail below.
BRIEF DESCRIPTION OF THE DRAWINGS
[0040] In the drawings:
[0041] FIG. 1 is a schematic view showing a barrier layer (left) with a definition or primary and secondary direction and a schematic view of layers of a fiber material arranged at an angle of 0°, 33° and −33°;
[0042] FIG. 2 is a perspective view showing an exemplary embodiment of a barrier layer arrangement according to the present invention with composite arrangement and compensation beads; and
[0043] FIG. 3 is a view showing the direction dependence of the modulus of elasticity (left) and of the coefficient of thermal expansion (right).
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0044] Referring to the drawings in particular, FIG. 1 schematically shows a barrier layer 1 , which is designed as an anisotropic composite or anisotropic, fiber-reinforced plastic. This means that the composite possesses direction-dependent properties, which are preset by the material parameters, especially the coefficient of thermal expansion α ΔT and the stiffness, which is indicated by the modulus of elasticity. These two parameters are relevant for the stresses and expansions occurring in the barrier layer at very low temperatures.
[0045] The composite of the barrier layer consists of oriented fibers embedded in a matrix. In order for the shrinkage of the barrier layer to occur essentially in one direction only, which is designated as the secondary direction 2 in FIG. 1 , the coefficient of thermal expansion α ΔT must be as high as possible, on the one hand, in a primary direction 3 extending at right angles to the secondary direction 2 , and the stiffness in the secondary direction 2 should also have a low value.
[0046] The thermal expansion of the barrier layer 1 is affected, among other things, by the selection of the fibers and the stiffness [and] by the design of the barrier layer.
[0047] The oriented fibers of the barrier layer 1 or of the composite are arranged in different layers over the thickness of the layer, the layers forming different angles with one another. Three layers 4 , 5 and 6 , which are arranged one on top of another and form an angle of 0°, 33° and −33°, respectively, with one another, are shown as an example on the right-hand side of FIG. 1 .
[0048] Carbon, polyethylene, aramid, PBO or glass fibers or another suitable material is used for the reinforcing material, while the matrix is manufactured, for example, from epoxy resin, polyester resin, polyurethane or another suitable material.
[0049] The fibers or fiber layers 4 , 5 and 6 may be formed exclusively from one fiber material, e.g., carbon fibers or glass fibers. The fiber material may also be mixed in hybrid embodiments, e.g., carbon fibers are used for a first layer and glass fibers for other layers.
[0050] The anisotropic composite layer is gas-tight due to the materials selected. It may be combined with other additional layers, e.g., connected to a gas-tight layer or a liner. To manufacture the fiber composite and barrier layer 1 , the fiber layers may be placed one over the other at preset angles and impregnated with the matrix and cured.
[0051] Furthermore, the layers may also be designed as prepregs, in which endless fibers, which may also be in the form of a fabric, are embedded in a still) uncured plastic matrix, the prepregs being placed one over another at an angle and connected to one another by supplying heat and applying pressure.
[0052] FIG. 2 shows an exemplary embodiment of the barrier layer 1 , which has a design that is described in connection with FIG. 1 , with a plurality of beads, which are oriented in the primary direction 3 , being located next to each other as compensators 7 in the secondary direction 2 .
[0053] If the barrier layer 1 is cooled as a wall of a tank for ultra cold liquids by filling said tank to a temperature in the range of −160° C. or lower, the anisotropic fiber composite brings about a temperature-dependent shrinkage 8 , which takes place in the secondary direction 2 only and is indicated by the broken line in FIG. 2 , due to a high modulus of elasticity and a very low coefficient of thermal expansion in the primary direction 3 and a simultaneously low modulus of elasticity and high coefficient of thermal expansion in the secondary direction 2 arranged at an angle of 90° in relation to the primary direction 3 .
[0054] The shrinkage 8 occurring in the secondary direction 2 only is compensated by an expansion 9 of the compensating beads 7 , and the barrier layer 6 has no stress peaks caused by intersecting beads in an isotropic fiber composite.
[0055] Various examples of the state of the art and of the present invention will be described below, which are listed in Table 1. UD designates unidirectional hybrid: carbon and glass fibers, C: carbon fibers, G: glass fibers, and CLT: classical laminate theory. The index s indicated for the angles in square brackets indicates that the laminates have a mirror-symmetrical design to avoid warpage. [0/45/−45/90]s correspondingly stands for [0/45/−45/90/90/−45/45/0], i.e., right layers.
[0000]
Coefficient of thermal
Modulus of
expansion [10 −6 /K]
elasticity
Determined
[MPa]
Material
experimentally
Calculation according to CLT
Fiber
Primary
Secondary
Primary
Secondary
Primary
Secondary
materials
Laminate design
(0°)
(90°)
(0°)
(90°)
(0°)
(90°)
Quasi-
Glass
[0 G , 45 G , −45 G , 90 G ] s
11.00
11.00
11.79
11.79
23,711
23,711
isotropic
Carbon
[0 C , 45 C , −45 C , 90 C] s
2.58
2.58
2.66
2.66
54,335
54,335
Anisotropic
Glass
[0 G , 45 G , −45 G ] s
8.03
11.76
8.79
17.35
26,102
16,785
[O G , 33 G , −33 G ] s
6.87
16.01
7.05
25.87
31,260
14,005
Hybrid
[0 C , 45 G , −45 G ] s
2.63
13.76
2.36
19.86
57,647
16,674
[0 C , 33 G , −33 G ] s
2.54
17.96
1.89
25.14
62,776
13,556
Carbon
[0 C , 45 C , −45 C ] s
—
—
0.09
6.74
60,476
26,015
[0 C , 33 C , −33 C ] s
—
—
−1.64
15.17
76,920
14,612
UD
Glass
[0 G , 0 G 0 G ]
6.21
17.49
7.36
31.76
44,480
13,219
Carbon
[0 C , 0 C , 0 C ]
0.25
25.11
0.25
31.54
139,280
9,560
UD Unidirectional
Hybrid Carbon and glass fibers
C Carbon fiber
G Glass fiber
CLT Classical Laminate Theory
[0056] As can be determined from Table 1, the values of 11.79×10 −6 /K are obtained for the coefficient of thermal expansion α ΔT and 23,711 MPa for the modulus of elasticity (modulus E) according to the classical laminate theory (CLT) for a quasi-isotropic design comprising eight layers, which are arranged one on top of another at the angles [0°, 45°, −45°, 90°]s with the use of glass fibers. The use of carbon fibers leads to the values of 2.66×10 −6 /K for α ΔT and 54,335 MPa for the modulus of elasticity according to the CLT.
[0057] The values of 7.36×10 −6 /K are obtained according to the CLT theory for α ΔT and 44,480 MPa for the modulus of elasticity in the primary direction 3 and the values of 31.76×10 −6 /K are obtained for α ΔT and 13,219 MPa for the modulus of elasticity in the secondary direction 2 for a unidirectional design, in which three layers are arranged one on top of another exclusively in the primary direction 3 in the case of glass fibers. In this arrangement, the values of 0.25×10 −6 /K are obtained for α ΔT and 139,280 MPa for the modulus of elasticity in the primary direction 3 and the values of 31.54×10 −6 /K and 9,560 MPa for the modulus of elasticity in the secondary direction 2 for carbon fibers.
[0058] An anisotropic design with six layers arranged one on top of another at the angles [0°, 45°, −45°]s has, according to the CLT, the values of 8.79×10 −6 /K for α ΔT and 26,102 for the modulus of elasticity in the primary direction 3 and 17.35×10 −6 /K for α ΔT and 16,785 MPa for the modulus of elasticity in the secondary direction 2 in the case of glass fibers. The values of 0.09×10 −6 /K and 60,467 MPa for the modulus of elasticity are obtained for carbon fibers in this arrangement in the primary direction 3 and the values of 6.74×10 −6 /K for α ΔT and 26,105 MPa for the modulus of elasticity are obtained in the secondary direction 2 .
[0059] The values of 7.05×10 −6 /Ka for α ΔT and 31,260 MPa for the modulus of elasticity are obtained according to the CLT in the primary direction 3 and the values of 25.87×10 −6 /K for α ΔT and 14,005 MPa for the modulus of elasticity are obtained in the secondary direction 2 for an anisotropic design with six layers arranged one on top of another at the angles [0°, 33°, −33°]s for glass fibers. The values of −1.64×10 06 /K for α ΔT and 76,920 MPa for the modulus of elasticity are obtained in the primary direction 3 and the values of 15.17×10 −6 /K for α ΔT and 14,612 MPa for the modulus of elasticity are obtained in the secondary direction 2 for carbon fibers in this arrangement.
[0060] The values of 2.36×10 −6 /K for α ΔT and 57,647 MPa for the modulus of elasticity are obtained according to the CLT in the primary direction 3 and the values of 19.86×10 −6 /K for α ΔT and 16,674 MPa for the modulus of elasticity are obtained in the secondary direction 2 in the case of an anisotropic hybrid design with six layers arranged one on top of another at the angles [0°, 45°, −45°]s, of which the layer in the primary direction 3 )(0° is made of carbon fibers and the layers extending at the angles 45° and −45° are made of glass fibers. The values of 1.89×10 −6 /K for α ΔT and 62,776 MPa for the modulus of elasticity are obtained according to the CLT in the primary direction 3 and the values of 25.14×10 −6 /K and 13,556 MPa for the modulus of elasticity are obtained in the secondary direction 2 for an arrangement at the angles of 0°, 33° and −33° in the case of the hybrid design.
[0061] The lowest coefficient of thermal expansion in the primary direction is attained with a [33°/−33°]s layer arrangement. An additional 0° layer increases the strength in the primary direction 3 .
[0062] While a quasi-isotropic layer arrangement has identical values for the modulus of elasticity and the coefficient of thermal expansion in the primary direction 3 and in the secondary direction 2 , a value of the quotient of the coefficient of thermal expansion in the secondary direction, divided by the coefficient of thermal expansion in the primary direction, can be adjusted to a value greater than 2 by selecting the materials and angles for the layers. In case of a negative quotient, the value of the quotient is preferably greater than 5 and especially preferably greater than 10.
[0063] The value of a quotient of the modulus of elasticity in the primary direction, divided by the modulus of elasticity in the secondary direction, can be set between 1.5 and 15 by selecting the materials and angles for the layers.
[0064] The above figures show only details of a barrier layer. A complete barrier layer can be manufactured in nearly any desired shape. For example, the barrier layer may be designed such as to be suitable for spherical, prismatic or cylindrical shapes. Composite shapes are possible as well.
[0065] FIG. 3 shows the modulus of elasticity (left) and the coefficient of thermal expansion (right) as a function of the direction. A distance 10 of a point 11 on the ellipse 12 corresponds to the modulus of elasticity in the corresponding direction. The coefficient of thermal expansion is shown in the same manner in the right-hand part of the figure. As can be recognized, the modulus of elasticity is markedly lower in the secondary direction 2 than in the primary direction 3 , and the coefficient of thermal expansion is markedly lower in the primary direction 3 than in the secondary direction 2 .
[0066] While specific embodiments of the invention have been 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. | A barrier layer arrangement for tank systems includes at least one layer made of a material that has anisotropic properties. The anisotropic properties can be specifically adjusted by way of the design of the layer and/or the material parameters. | 5 |
FIELD OF THE INVENTION
[0001] The present invention relates to an apparatus, system and method for electrostatically coating substrates with resins for use as prepregs in producing composite materials.
BACKGROUND OF THE INVENTION
[0002] A prepreg is a substrate pre-impregnated with a matrix resin that binds together the fibers of the substrate. Prepregs are precursor materials that can be used to make finished composite components for inclusion in a wide range of applications, such as airplane structures, medical products, printed circuit boards, industrial components, recreational products and commercial vehicles. In general, composites have advantages over competing materials such as metals. Among other attributes, prepregs generally have higher specific strength, better corrosion resistance, and allow for faster assembly.
[0003] The use of composite components made from advanced thermoplastic prepregs is relatively recent. Composites are available in a wide range of substrates and thermoplastic resins. The substrate is often a carbon, glass or aramide substrate, while typical resins include polyethylene (PE), polypropylene (PP), polyetheretherketone (PEEK), polyethersulfone (PES), polyphenylsulfone (PPS), polyimide (PI), polyamides (PA), polycarbonate (PC), polyethylene terephthalate (PET), polyurethane (PU), polyester and fluoropolymers. Thermoplastic prepreg fabrics typically have inherent toughness, good viscoelastic damping, indefinite shelf life, chemical resistance, assembly flexibility and recycling capabilities.
[0004] Thermoplastic prepregs can be prepared using solvent impregnation, hot melt coating, film stacking, as well as other methods. However, chemical resistance of the resin often makes solvent impregnation difficult. Hot melt coating, a process similar to pultrusion, requires resins with moderate to high viscosity and melt temperatures. In addition, it often requires high-pressure pumps and resin meters.
[0005] Film stacking uses thin films of dry thermoplastic resins that are sandwiched or stacked together with the fabric. After sandwiching, the stack is consolidated under heat and pressure. While this method is clean and solvent-free, consolidation must be carefully carried out to fully impregnate the fabric. The cost of these thin film resins is often relatively high, especially when resins like PEEK and PPS are employed.
[0006] Dry powder deposition methods, primarily the electrostatic fluidized bed (EFB) method, are at least 30 years old. Their use obviates the processing difficulties of wet systems (wetting, flow, and homogeneity). In the EFB method, powdered resin particles are aerated in a fluidized chamber and are electrostatically charged by ionized air forced through a porous plate at the base of the chamber. As the powder particles are charged, they repel each other to such a degree that they rise above the chamber forming a low-velocity, essentially uniform cloud of charged particles.
[0007] When a substrate is passed over or conveyed through this cloud, the charged powder particles are attached to it because of the potential difference between the particles and substrate. As the particles become attached to the substrate, the particles form a coating whose thickness and deposition rates are controlled both by the magnitude of the applied voltage in the air ionization process and by the exposure time of the substrate to the cloud. Because of the large potential difference between the charging media and most substrates, even natural insulators can be coated. Once coated with particles, the substrate is transported through an oven where the powder melts, flowing over the substrate.
[0008] Reference is now made to FIG. 1 where a schematic illustration of a typical prior art EFB coating apparatus 110 is presented. It is composed of a dry air input 12 through which dry air enters into an air plenum chamber 14 . The latter is situated under a charging medium (plate) 16 that is connected to a high-voltage DC power supply 18 . The incoming dry air is blown past charging medium 16 and through porous plate 20 on which powdered resin is placed. The charged air transfers charge to the powdered resin and forms a low-velocity cloud of charged particles 22 that attaches itself to a grounded substrate 24 .
[0009] While FIG. 1 shows an object being electrostatically coated, it is readily apparent to one skilled in the art that fabric, tow, tube, tape or fiber substrates can also be coated when such substrates are drawn between two fluidized beds disposed symmetrically on either side of the substrate. FIG. 1 does not show the heating apparatus that melts the polymer resin particles electrostatically attached to the substrate. Typical substrates that can be coated by such an apparatus are fiberglass, carbon fibers and aramide materials.
[0010] There are drawbacks to the EFB method. Difficulties exist because the porous plate in fluidized bed coating systems often becomes blocked, resulting in a non-uniform distribution of the charged powder across the coated substrate. In addition, the holes in EFB porous plates can never be fabricated with sufficient uniformity to ensure homogeneity of the coating. Moreover, low-velocity particles generally coat only the surface of a substrate and cannot penetrate into the spaces or interstices of the substrate. Prepregs produced by this method have relatively high resin coating loads. As a result, when such coated fabrics are used to form composites, the composite layers do not adhere to each other uniformly and the composites are generally of low quality.
Definitions
[0011] Except where noted otherwise, in what is discussed herein, the following terms will be used with the following meanings:
[0012] Substrate—fabric, often a web-type fabric, fiber, strand or tow material. In certain instances, the word “fabric” may be used to indicate any type of substrate.
[0013] Tow—a bundle of untwisted continuous filaments.
[0014] Strand—twisted continuous filaments.
[0015] Prepreg—a substrate pre-impregnated with a matrix resin, the resin acting to bind together the fibers of the substrate.
[0016] Composite—two or more layers of prepregs to which heat and pressure have been applied, thereby causing the matrix resin in the several prepreg layers to fuse and form an integral object.
[0017] Resin load—the mass of resin deposited per unit area or per unit mass of substrate.
SUMMARY OF THE PRESENT INVENTION
[0018] Applicant has realized that an apparatus, herein called an “acceleration cell,” emitting charged resin powder at high velocity (“forced flow”), that does not include a porous plate and has a wide aperture, solves many of the problems found in the prior art. Applicant has determined that such a cell produces a uniform coating with lower resin loads, as well as increased resin powder penetration of the substrate. The cell can employ either frictional or high-voltage direct current (DC) power source methods to charge the resin powder. Alternatively, a single acceleration cell can use both methods simultaneously. Systems using a plurality of such cells can employ both power source charging and friction-charging concurrently. A coating method using such cells is described.
[0019] It is an object of the present invention to provide an apparatus, system and method for preparing uniformly coated prepreg substrates to be used in producing composites.
[0020] It is yet a further object of the invention to prepare prepregs with the coating penetrating more deeply into the substrate.
[0021] It is yet another object of the invention to form prepregs with resin loads smaller than those in prepregs prepared by other dry methods, particularly the electrostatic fluidized bed method.
[0022] It is yet another object of the invention to provide large-area coated substrates having uniform coatings, smaller resin loads and deeper coating penetration.
[0023] It is a further object of the present invention to more readily use micron-size resin particles in fabricating prepregs.
[0024] Other objects of the present invention will become apparent from the following embodiments of the present invention.
[0025] There is thus provided in accordance with the present invention an acceleration cell for coating a substrate with plastic resin particles which includes a housing having first and second ends, the first end containing an air inlet port and the second end an air outlet port. The housing further includes a particle feed port, which is formed in a wall of the housing between the inlet and outlet ports. The feed port is connected to a plastic resin particle source. The housing receives a carrier flow of air from the inlet port, which exits through the outlet port. The carrier flow takes up the resin particles delivered via the particle feed port, so that there is an outflow of the resin particles suspended in the carrier flow. The outlet port has a generally wide configuration with a width that is predetermined so as to correspond to the width of a substrate being coated. This allows the suspended resin particle outflow to deliver the resin particles across the entire width of the substrate. The acceleration cell also contains at least one electrostatic charger positioned in the housing which charges the particles suspended in the carrier flow. In addition, associated with the housing is at least one apparatus for accelerating the carrier flow and charged particles suspended in the flow through the housing. Additionally, the cell includes at least one flow-modifying apparatus disposed within the housing for modifying the suspended resin particle outflow so as to cause a uniform spatial distribution of the resin particles exiting from the cell, thereby producing a uniform spatial delivery of particles across the substrate.
[0026] In accordance with one embodiment of the present invention, the at least one flow-modifying apparatus is a turbulence-producing means. In some embodiments the turbulence-producing means is a plurality of deflectors; in other embodiments, the turbulence-producing means is a plurality of baffle-like elements producing sufficient turbulence to ensure the desired degree of uniformity in the spatial distribution of the exiting particles.
[0027] In further embodiments, the at least one flow-modifying apparatus is a plurality of airflow vanes. In some embodiments the length of these vanes is about 3 to 7 times the distance between adjacent vanes, while in other embodiments their length is about 4 to 6 times the distance between nearest neighbors.
[0028] In yet another embodiment, the length to height ratio (L/H) of the housing is between about 1 to about 10, where length L is the distance between the side of the at least one flow-modifying apparatus distal to the proximate side of a nozzle region of the housing, and the proximate side of the nozzle region. The height H is the distance between opposite surfaces of the housing in the region defining length L; the height H is taken along a direction generally parallel to the shorter side of the air outlet port. In another embodiment, the length to height (L/H) ratio is between 3 to 5.
[0029] Additionally, in another embodiment of the invention the at least one apparatus for accelerating the carrier flow and charged particles suspended in the flow is at least one sloped wall of the housing, the sloped wall narrowing the housing in the direction of the air outlet port. In some embodiments of the invention, the sloped wall of the housing has a slope that can range up to about 40 degrees, while in other embodiments the slope can range up to 15 degrees.
[0030] In a further embodiment of the invention, the slope of the at least one sloped wall is discontinuous as the wall proceeds in the direction of the air outlet port.
[0031] In yet another embodiment, the at least one apparatus for accelerating the carrier flow and charged particles suspended in the flow is a Venturi constriction, the Venturi constriction producing a pressure differential between the area in, and adjacent to, the constriction and the plastic resin particle source, thereby bringing the resin particles into the housing through the particle feed port.
[0032] Additionally, in an embodiment of the present invention, the at least one apparatus for accelerating the carrier flow and charged particles suspended in the flow is at least one electrically charged surface having a charge opposite to the charged particles.
[0033] In still another embodiment, the at least one apparatus for accelerating the carrier flow and charged particles suspended in the flow further includes a means for generating a magnetic field, the field increasing the uniformity of the spatial distribution of the particles exiting from the air outlet port.
[0034] In other embodiments the at least one apparatus for accelerating the carrier flow and charged particles suspended in the flow is a blower.
[0035] In a further embodiment of the invention, the air outlet port is a rectangular slot aperture characterized by at least one of the following: an aspect ratio ranging from about 1 to about 3000, and a length of at least 2 mm. In another embodiment of the invention, the air outlet port is a rectangular slot aperture characterized by at least one of the following: an aspect ratio ranging from about 1 to about 200, and a length of at least 50 mm.
[0036] In still another embodiment of the invention, the air outlet port is a conic section shaped aperture, where the aperture is characterized by at least one of the following: a major to minor axis ratio ranging from about 1 to about 3000, and a major axis of at least 2 mm. In another embodiment of the invention, the air outlet port is a conic section shaped aperture, where the aperture is characterized by at least one of the following: a major to minor axis ratio ranging from about 1 to about 200, and a major axis of at least 50 mm.
[0037] In yet another embodiment of the invention, the at least one electrostatic charger includes a high-voltage power source that applies voltage to at least one chargeable surface, the chargeable surface providing charge to the carrier flow of air in the housing, the charge then being transferred to the resin particles. In an embodiment of the invention, the at least one chargeable surface is at least one brush. In yet another embodiment of the invention, the at least one charger is at least one friction-charging surface.
[0038] Additionally, in another embodiment of the invention, at least one friction-charging surface includes at least one surface selected from the following list of surfaces: at least one planar surface, at least one undulating surface, at least one roughened surface, and at least one smooth surface.
[0039] In a further embodiment of the invention, the cell includes both at least one friction-charging surface and at least one high-voltage power source that applies voltage to at least one chargeable surface, the chargeable surface providing charge to the carrier flow of air in the housing, which is then transferred to the resin particles. In some embodiments these components can be used in series and in others in parallel.
[0040] Additionally, in an embodiment of the invention, the second end of the housing is a detachable sleeve with the sleeve being replaceable with another sleeve having an air outlet port of a different size. In other embodiments, the second end of the housing is a sleeve with an air outlet port, the size of the outlet port being variable.
[0041] In an embodiment of the invention, the cell further includes a humidity controller.
[0042] Additionally, in yet another embodiment of the invention, the average velocity of the particles is at least 0.1 m/s as they exit the air outlet port of the cell, while in still another embodiment, the average velocity of the particles is at least 0.5 m/s as they exit the air outlet port of the cell.
[0043] Additionally, there is provided in accordance with the present invention a system for coating a substrate with plastic resin particles, the system including a coating chamber and at least one acceleration cell constructed according to any one of the previous embodiments. The at least one cell jets charged resin particles at high velocities into the coating chamber through an air outlet port of the acceleration cell. The system also includes a substrate positioned in the coating chamber on which the jetted high-velocity charged resin particles are deposited. In addition, the system contains a heat source for melting the resin particles deposited on the substrate, whereby the melted resin coats the substrate.
[0044] In an embodiment of the present invention, the substrate positioned in the chamber is moving.
[0045] In a further embodiment of the present invention, the average velocity of the jetted particles as they exit the air outlet ports is at least 0.1 m/s. In other embodiments, the velocity is at least 0.5 m/s.
[0046] Further, in accordance with another embodiment of the present invention, the at least one acceleration cell is at least two acceleration cells. In some embodiments, at least one of the at least two acceleration cells charges the particles by friction and at least one of the at least two acceleration cells charges the resin particles by using a high-voltage power source.
[0047] Additionally, in another embodiment of the present invention, the at least one acceleration cell charges the resin particles by friction.
[0048] In another embodiment of the present invention, the at least one acceleration cell charges the resin particles by using at least one high-voltage power source.
[0049] Further, in an embodiment of the present invention, the at least one acceleration cell includes both friction-charging components and high-voltage power source charging components, and the cell charges the resin particles by at least one of these methods. Additionally, in an embodiment of the invention, the frictional and high-voltage components are used in series, while in another embodiment they are used in parallel.
[0050] In still another embodiment of the present invention, the substrate is charged so as to attract the jetted charged particles entering the coating chamber from the at least one acceleration cell, thereby further accelerating the particles. In some embodiments, the substrate is charged by moving it past at least one contacting plastic body, while in others it is charged by a power source.
[0051] In a further embodiment of the present invention, the coating chamber further includes at least one charged element positioned substantially opposite the air outlet port of the at least one acceleration cell so as to attract and accelerate the jetted charged particles emitted from the acceleration cell.
[0052] In still another embodiment of the present invention, the system further includes a computerized control system for control of the active elements which regulate at least one of the following parameters: charging voltage, speed of conveyance of the substrate, speed of the carrier flow in the acceleration cells, size of the air outlet port, quantity of resin particles brought into the cell, output voltage and output current. The control system is in communication with sensors in the system, the sensors sensing the values of at least one of the above parameters. Based on the sensed values, the computer adjusts the values of the parameters by communicating the optimizing values to the active elements.
[0053] In yet another embodiment, the system further includes a humidity controller.
[0054] In a further embodiment, the orientation of the at least one acceleration cell is such that the particles emitted from the air outlet port of the cell impinge the substrate substantially perpendicularly.
[0055] In still another embodiment of the present invention, the orientation of the at least one acceleration cell is such that the particles emitted from the air outlet port of the cell impinge the substrate at a generally non-perpendicular angle.
[0056] Further, in accordance with the present invention, a plane containing the air outlet port of the acceleration cell makes an angle of between about 60 and about −60 degrees with respect to the normal to a plane of the substrate, the plane of the substrate being the plane being coated.
[0057] Additionally, there is provided in accordance with the present invention a method for coating a large-area substrate where the method includes the steps of:
[0058] positioning the substrate in a coating chamber;
[0059] accelerating charged resin particles through an air outlet port of at least one acceleration cell, the acceleration cell being constructed as described above, the particles impinging and depositing on a wide swath of the substrate, the particles moving with a velocity of at least 0.1 m/s as they exit the air outlet port; and
[0060] melting the deposited resin particles, thereby coating the substrate.
[0061] In another embodiment of the invention, the positioning step of the method includes moving the substrate through the chamber.
[0062] Further, in accordance with another embodiment of the present invention, during the accelerating step of the method, the particles coat continuous wide swaths of a continuously moving substrate.
[0063] In still another embodiment of the invention, the method also includes the step of attracting the charged particles toward the substrate.
[0064] In yet another embodiment of the method of the present invention, the method includes a second accelerating step where the first accelerating step accelerates particles having diameters equal to or less than a predetermined diameter, while the second accelerating step accelerates particles having diameters greater than the predetermined diameter. In some embodiments, this predetermined diameter is 5 microns.
[0065] In a further embodiment of the invention, the positioning step of the method includes positioning a web-like substrate that is moving through the coating chamber.
[0066] In another embodiment of the invention, the particles exit the air outlet port with a velocity of at least 0.5 m/s.
BRIEF DESCRIPTION OF THE DRAWINGS
[0067] The present invention will be understood and appreciated more fully from the following detailed description taken in conjunction with the drawings in which:
[0068] [0068]FIG. 1 is a schematic cross-sectional view of a typical prior art fluidized bed coating apparatus;
[0069] [0069]FIG. 2 is a schematic side view illustration of a coating line incorporating a coating apparatus and system constructed in accordance with a preferred embodiment of the present invention;
[0070] [0070]FIG. 3 is a side view illustration of a coating chamber constructed and operative according to an embodiment of the present invention;
[0071] [0071]FIGS. 4A and 4B are isometric views of a high-voltage charging acceleration cell and coating chamber constructed in accordance with a preferred embodiment of the present invention;
[0072] [0072]FIGS. 5A and 5B are schematic side and top views, respectively, of an acceleration cell using high-voltage to charge resin powder, constructed in accordance with a preferred embodiment of the present invention;
[0073] [0073]FIGS. 6A and 6B are schematic side and top views, respectively, of an acceleration cell using friction to charge resin powder, constructed according in accordance with a preferred embodiment of the present invention;
[0074] [0074]FIGS. 7A-7C are respectively top-side, top and side schematic views of a nozzle suitable for use in acceleration cells constructed according to embodiments of the present invention;
[0075] [0075]FIG. 8 is a schematic cut-away, top-side view of a portion of an acceleration cell constructed in accordance with a preferred embodiment of the present invention; and
[0076] [0076]FIGS. 9A, 9B and 9 C are top-side and top views, respectively, of turbulence-producing elements for use with the embodiment shown in FIG. 8.
[0077] Similar elements in the Figures are numbered with similar reference numerals.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0078] Prepregs currently used to form composite materials are often characterized by very non-uniform plastic resin coatings, high resin loads and little penetration of the substrate by the resin. Applicant has realized that the use of high-velocity (“forced flow”) charged resin particles ejected from an acceleration cell that electrostatically charges such particles can obviate these problems. Applicant has developed a cell for coating wide area substrates where the cell has a uniformly charged resin particle discharge stream. The particles constituting the discharge stream are traveling at relatively high velocities compared to prior art dry coating systems. Uniformity and velocity are maintained by means which include, but are not limited to, blowers, Venturi constrictions, turbulence-producing baffles, air control vanes, and a decreasing internal cross-sectional area of the cell in the direction of the cell's wide aperture. The acceleration cells discussed hereinbelow can employ, separately or concurrently, either high-voltage power source electrical charging or friction-charging methods. The acceleration cells can be used in coating systems described herein; a method for using these cells and systems for coating large-area, continuously moving substrates, is also described. The system is particularly useful for use with small micron-size resin particles, the fabrication of which has recently been improved, and for which increased future usage is expected.
[0079] Reference is now made to FIG. 2 in which is illustrated a schematic view of a typical coating line, referenced generally 210 , incorporating a coating apparatus and system constructed and operative in accordance with a preferred embodiment of the present invention. A substrate referenced 38 is led from a pay-off roller 32 to a take-up roller 34 . Optionally, the substrate can be passed through a wetting station 30 , which moistens substrate 38 , improving the subsequent attachment of charged powder to substrate 38 . Wet station 30 will most beneficially be used when substrate 38 is an aramide or glass substrate. The substrate is then passed through a coating chamber 36 and a heating means 28 . Substrate 38 , typically a carbon, glass, or aramide substrate such as Kevlar®, is guided along line 210 by a plurality of control rollers 40 , some of which are nip rollers 40 A. Nip rollers 40 A also assist in controlling the speed of substrate 38 as it traverses coating line 210 .
[0080] Two electrostatic acceleration cells 12 A and 12 B, having wide apertures 46 A and 46 B respectively, are positioned substantially opposite each other in coating chamber 36 . Acceleration cells 12 A and 12 B charge resin powder particles brought into the cell as described below. While not readily seen in FIG. 2, acceleration cells 12 A and 12 B protrude into chamber 36 ; this can be better seen in FIGS. 3, 4A and 4 B discussed hereinbelow. The charged powder exiting from acceleration cells 12 A and 12 B at apertures 46 A and 46 B, enters coating chamber 36 , impinges on moving substrate 38 at high velocities, and adheres electrostatically to substrate 38 .
[0081] In FIG. 2, apertures 46 A and 46 B of acceleration cells 12 A and 12 B are shown to be substantially co-linear with each other and perpendicular to the path of the substrate. In other embodiments, while the main portion of each of acceleration cells 12 A and 12 B may be independently oriented perpendicularly to the path of the substrate, nozzles 23 A and 23 B of cells 12 A and 12 B can be angularly displaced with respect thereto. Preferably, however, nozzles 23 A and 23 B are oriented so as to project particles perpendicularly to the path of the substrate.
[0082] In FIG. 2, wide aperture acceleration cells 12 A and 12 B use high-voltage supplied by DC power supplies 14 A and 14 B to charge a preselected resin powder stored at powder storage boxes 24 A and 24 B. Powdered resin 25 A and 25 B is brought into cells 12 A and 12 B through powder tubes 50 A and 50 B from powder boxes 24 A and 24 B at Venturi constrictions 22 A and 22 B formed in respective cells 12 A and 12 B. As air is accelerated in cells 12 A and 12 B, as by use of a pair of air blowers 18 A and 18 B, past Venturi constrictions 22 A and 22 B, a drop in pressure is produced at constrictions 22 A and 22 B. This decrease in pressure causes a pressure differential to exist between constrictions 22 A and 22 B and the interior of powder boxes 24 A and 24 B, thereby drawing powder up into cells 12 A and 12 B.
[0083] Blowers 18 A and 18 B blow dry air into cells 12 A and 12 B via inlets, respectively referenced 15 A and 15 B, past brushes, respectively referenced 16 A and 16 B, mounted within cells 12 A and 12 B, as shown. Brushes 16 A and 16 B, typically made of brass or iron, are connected to high-voltage DC power supplies 14 A and 14 B. Brushes 16 A and 16 B facilitate the charging of the moving air, which in turn transfers charge to the powdered resin. The charged air and resin particles are accelerated toward coating chamber 36 as they pass through Venturi constrictions 22 A and 22 B. Between Venturi constrictions 22 A and 22 B and apertures 46 A and 46 B, at least part of the charged air transfers charge to the powdered resin. While the air-moving means driving air through inlets 15 A and 15 B have been exemplified as air blowers, other suitable means could also be used, in accordance with alternative embodiments of the present invention.
[0084] Coating chamber 36 is typically a plastic cylindrical chamber, into which acceleration cells 12 A and 12 B protrude, and has formed therewith a powder basin 58 into which unattached resin powder falls. The powder collected in powder basin 58 may then be returned via intermediate powder storage boxes (not shown) and a filtration device (also not shown) to powder boxes 24 A and 24 B from which it is again drawn into acceleration cells 12 A and 12 B.
[0085] Coating chamber 36 is also formed with ports 39 A and 39 B through which substrate 38 enters and exits coating chamber 36 . Near exit port 39 B there is a vacuum port 56 connected to vacuum powder collector 26 that collects the loose, excess powder in chamber 36 . The vacuum can be used to fine tune the resin load on substrate 38 , as by thinning out the resin particle layer on substrate 38 by removing poorly attached resin powder from substrate 38 as substrate 38 exits chamber 36 .
[0086] Substrate 38 , covered with electrostatically attached powdered resin, then advances to heating means 28 where the resin is melted, allowing the resin to flow over substrate 38 . Typically, but without being limiting, heating means 28 can be any of the large number of commercially available hot air or IR ovens. Substrate 38 is then led to take-up roller 34 via a pair of nip rollers 40 A.
[0087] Acceleration cells 12 A and 12 B employ high-voltage DC power supplies 14 A and 14 B to charge the resin particles. The cells and their operation are described in more detail in conjunction with FIGS. 5A and 5B below. In other embodiments, acceleration cells employing friction-charging means can be used to charge the resin powder. Such cells are similar to the ones described above and are described in more detail in conjunction with FIGS. 6A and 6B below.
[0088] Referring now to FIGS. 3, 4A and 4 B, there is seen a coating apparatus 310 , constructed in accordance with a preferred embodiment of the present invention. The illustrated components are similar to those shown and described above in conjunction with FIG. 2. Similar components are therefore referenced by similar numerals, and are not specifically described again except as may be necessary to gain a further understanding of the present embodiment. Acceleration cell 12 A uses a high-voltage DC power source (not shown) to charge resin powder. The cell has a wide aperture 46 through which powder is projected into coating chamber 36 . While shown in FIGS. 3 and 4A, second acceleration cell 12 B is truncated and not presented in a cut-away view. Powder basin 58 catches powder that enters chamber 36 but which fails to attach to the substrate. A vacuum apparatus (not shown) removes all resin powder that does not adhere tightly to substrate 38 and that is found loose within chamber 36 through vacuum port 56 .
[0089] Referring now to FIGS. 5A and 5B, there is shown, in schematic form, the acceleration cell 12 as shown and described above in conjunction with the embodiment of FIGS. 2-4B, in accordance with a preferred embodiment of the invention. Acceleration cell 12 charges dry air using a high-voltage DC power source (not shown). Cell 12 includes brushes 16 attached to leads 57 ; the brushes increase the efficiency of charging the air as it is forcibly blown through cell 12 by a blower (not shown). The dry ionized air blown through cell 12 flows through Venturi constriction 22 where it is accelerated toward aperture 46 .
[0090] Powder is introduced into cell 12 , substantially as described above in conjunction with FIGS. 2, 3, 4 A and 4 B, from a powder box 24 (FIGS. 2 and 3) through powder tube 50 (FIGS. 2 and 3) via powder feed ports, referenced 52 , formed proximate to Venturi constriction 22 . Powder feed ports 52 are most clearly seen in FIG. 5B.
[0091] After entering cell 12 , the resin powder acquires electrostatic charge from the ionized air, the latter also serving as a carrier medium for the charged powdered resin. A series of airflow control vanes 54 , most clearly seen in FIG. 5B, is located in the forward part of cell 12 that lies between the Venturi constriction 22 and aperture 46 . Typically, but not necessarily, the vanes are positioned in the nozzle portion 23 of cell 12 . Vanes 54 are important to assure a uniform discharge stream of particles as the particles exit cell 12 and enter coating chamber 36 . In order to improve uniformity, the length of the vanes is typically 3 to 7 times the distance between adjacent vanes, preferably 4 to 6 times the distance between nearest neighbor vanes.
[0092] Another embodiment of an acceleration cell includes several smaller vanes (not shown) formed between vanes 54 , shown in FIG. 5B, in a region close to aperture 46 . In yet other embodiments, vanes 54 extend from nozzle portion 23 in the direction of Venturi constriction 22 , reaching mixing region 27 discussed below.
[0093] As seen in FIGS. 5A and 5B, a plurality of deflectors 53 is formed on a base portion 51 , thereby to define within cell 12 a mixing region, referenced generally 27 . The provision of the deflectors 53 gives rise to turbulent flow, thereby to improve the uniformity of the spatial distribution of the particles. These deflectors are shown and described in greater detail below with reference to FIGS. 8, 9A and 9 B. While deflectors have been described as the turbulence-producing means above, any baffle-like elements, or other turbulence-generating means disposed in any manner could also be used, provided the desired degree of uniformity is attained. More generally, any means can be used that produces a uniform distribution of particles in the discharge stream exiting from the cell through its wide aperture.
[0094] Acceleration cells 12 , as depicted in FIGS. 5A and 5B, show the interior walls of a stabilization region 29 to be formed as a first sloped portion S 3 , and a second, more sharply sloped portion S 2 contiguous therewith, formed within nozzle 23 , proximate to aperture 46 . These sloped portions are described hereinbelow with reference to FIGS. 7A-7C, 8 , 9 A and 9 B.
[0095] As described above, Venturi constriction 22 is provided so as to generate a pressure reduction in the region of the constriction that allows for the introduction of resin powder into acceleration cell 12 , accelerating the powder therein. It will be appreciated that the Venturi constriction 22 can be located at any position along the length of acceleration cell 12 between brushes 16 and mixing region 27 . Furthermore, it will be readily apparent to one skilled in the art that other methods for introducing the resin into the cell are also possible. Examples of such other methods include the placement of powder in a powder box above acceleration cell 12 , the powder box being shaken so as to cause a gravity feed into the cell. Additionally, any vacuum-producing device attached to the powder box could be used to draw powder into the cell.
[0096] Since ensuring coating uniformity is critical, acceleration cell 12 of FIGS. 5A and 5B is typically constructed so that the length (L) of the cell from the beginning of the mixing region to the beginning of the nozzle region is 1-10 times, and preferably 3-5 times, the height (H) of the cell. For purposes of this ratio, the height of the cell is defined as the distance along the y-axis as shown in FIGS. 5A and 5B in the region defined by L above. Similarly, uniformity typically requires an aspect ratio of wide aperture 46 of 1-3000, and preferably 1-200. The aspect ratio is herein defined as the ratio of the aperture's longer dimension to its shorter dimension e.g. length to width or major to minor axes. Typically, the aperture's longest dimension, its length, can range from at least 2 mm, preferably from at least 50 mm, to 1.8 meters, or even more.
[0097] While slot-like apertures, i.e. rectangular apertures, are generally used and have been described in the embodiments above, elliptical apertures of suitable dimensions can also be used. Similarly, circular apertures of wide enough radii can be employed. Apertures having tooth-shaped baffles positioned across their face can also be used.
[0098] Referring now to FIGS. 6A and 6B, there is shown, in schematic form, the acceleration cell 12 as shown and described above in conjunction with the embodiment of FIGS. 3-4B, in accordance with an alternative preferred embodiment of the invention, and in which resin powder is charged by friction. Arranged within cell 12 is a wave plate 59 , typically constructed from a plastic material like Teflon or nylon, which has an undulating surface 60 . Air is blown by a blower (not shown) from an opening 15 in end 64 of acceleration cell 12 past a Venturi constriction 22 , so as to cause a drop in pressure, generally as described above in conjunction with FIG. 2, thereby to cause resin powder to be drawn from a powder box 24 (FIG. 2) through tube 50 (FIG. 2) into cell 12 . The powder transported by the moving air moves past the undulating surface 60 of wave plate 59 , where the powder is charged by friction. The powder is then expelled through aperture 46 into coating chamber 36 , the latter best seen in FIGS. 2-4B. The likelihood of clogging in cell 12 is reduced because undulating surface 60 is spaced far enough away from the inside surface of housing 62 . Additionally, clogging is mitigated and the charged particle distribution made more uniform because undulating surface 60 provides for non-streamline flow.
[0099] Typically, the inside surface of housing 62 is formed having a textured surface, while the surface 60 of wave plate 59 is made to be generally smooth. Both housing 62 and wave plate 59 are generally fabricated from plastic. The inside surface of housing 62 , or the housing 62 itself, and wave plate 59 can be made from the same or different plastics. The nature of the plastics employed determines whether the charge on the resin powder will be positive or negative. Typical plastics that can be used are Teflon®, nylon, propylene, and acrylics. The aforementioned list is exemplary only and not intended to be limiting. It is readily apparent to one skilled in the art that the speed of the particles across the friction-charging surfaces 60 and 62 is an important factor in determining the efficacy of charging.
[0100] As in the embodiment of FIGS. 5A and 5B, the present embodiment also has a mixing region 27 having deflectors 53 positioned on a base 51 . Their construction and function are similar to deflectors 53 in mixing region 27 described with FIGS. 5A and 5B and discussed in greater detail with FIGS. 8, 9A and 9 B below. In addition, also as described in FIGS. 5A and 5B, FIG. 6A shows a slope S 3 in stabilization region 29 and an even sharper slope S 2 in nozzle 23 near aperture 46 . These slopes will be discussed further with reference to FIGS. 7A-7C, 8 and 9 A and 9 B.
[0101] As is apparent from the descriptions of the embodiments associated with FIGS. 5A, 5B, 6 A and 6 B, the present invention uses a high-pressure, high-velocity stream (“forced flow”) of charged resin powder. This “forced flow” stream ensures greater coating uniformity and penetration of the substrate than is possible with low pressure, low-velocity charged resin clouds, such as those used in prior art fluidized bed coaters. Furthermore, the acceleration cells of the present invention have typically long, narrow apertures, which can continuously coat large moving swaths of substrate. Other high-velocity coating devices generally use small diameter circular apertures with narrow beam widths, making uniform coating of large-area substrates difficult. Penetration into the substrate is also improved because the acceleration cells constructed according to the present invention can employ micron-size particles. The velocity of the charged particles as they exit the wide aperture of the acceleration cell is at least 0.1 m/s, preferably between about 1 to about 10 m/s. The maximum velocity will generally be that velocity that begins to cause deterioration in the substrate.
[0102] Electrostatic fluidized bed (EFB) coaters, such as the one shown in FIG. 1, employ particles that have low velocities. Clouds of such particles have a layered distribution. Heavier particles tend to settle and make up a greater percentage of the lower layers of an EFB particle cloud, while smaller particles make up a greater portion of the upper strata. As a result, it is readily apparent that when a substrate moves perpendicularly to the airflow in an EFB coater, the coating can never be entirely uniform. This situation does not occur with embodiments of the present invention.
[0103] While in the embodiments of the system shown in FIGS. 2, 3, 4 A and 4 B two acceleration cells are used as described in FIGS. 5A-6B, three or more cells may also be used in accordance with further embodiments of the invention.
[0104] Typically, both cells of the embodiments discussed with FIGS. 2-4B are of the same type, either frictional or electrical charging cells. However in other embodiments, the coating systems described herein employ at least one friction-charging cell and at least one electrical charging cell, concurrently.
[0105] In yet other embodiments, the mechanisms for both types of charging can be positioned in a single cell housing and the two types of mechanisms can be used in parallel or serially. Typically, but without being limiting, when used in parallel, each of the two different charging mechanisms can be positioned side by side, parallel to the long axis of the cell.
[0106] When used in series, the portion of the cell on the side of the Venturi constriction distal from the wide aperture is typically constructed as shown in FIGS. 5A and 5B with a brush element connected to a DC power source. The portion of the cell between the Venturi constriction and the wide aperture is constructed as in FIGS. 6A and 6B with a wave plate. Powder brought into the cell is thus first charged by ionized air previously charged by the brushes; the powder then undergoes charging by friction at the wave plate.
[0107] In yet another embodiment, the two mechanisms can be used serially with the resin particles first charged by friction and then by electrically charged brushes. In such an embodiment, both the frictional wave plate and the charged brushes are typically placed between the Venturi constriction and the wide aperture of the cell. In this last embodiment, the brushes generally lie closer to the wide aperture and the wave plate closer to the Venturi constriction. It should be understood that the configurations in the embodiments describing serial and parallel usage hereinabove is exemplary only and not intended to be limiting.
[0108] The capability of using both methods of charging concurrently, as described in the preceding embodiments, is particularly advantageous. The ability of certain plastic resins to be charged by friction is more limited than others. Using high-voltage charging would obviate the difficulty. On the other hand some plastics are relatively easily charged by friction and high-voltage charging would be unnecessary. Additionally, small micron-size particles are more easily charged by friction than larger particles. The use of micron-size resin particles will become more prevalent because of recent improvements in their manufacture. If a resin with a wide particle size distribution is used, the capability of charging by both methods simultaneously, as described in the last embodiments, will make charging, and the entire coating system, more efficient.
[0109] Since high particle velocity is important to ensure coating uniformity and particle penetration of the substrate, various means can be used to increase the velocity of the charged resin particles. Some of these means can be positioned in the acceleration cell, while others can be added to the coating system.
[0110] Charging the substrate with a polarity opposite to that of the impinging charged resin particles can increase velocity. The substrate can be charged by contacting it with a plastic body, such as a plastic plate or plastic roller, as the substrate moves through the coating chamber. Alternatively, the substrate can be charged directly using a high-voltage power supply.
[0111] Another means to increase particle velocity is best illustrated in the embodiment shown in FIG. 4A. Particle velocity can be enhanced by placing a conductive metal strip 47 in coating chamber 36 , substantially opposite wide aperture 46 of acceleration cell 12 . Strip 47 is charged oppositely to that of the resin particles via contacts 49 located on the outside of chamber 36 . Accordingly, strip 47 attracts and accelerates the particles toward the intervening substrate (not shown).
[0112] Electrostatically charged plates, sometimes used in conjunction with magnetic fields, can be appropriately positioned within the acceleration cells or within the coating chamber to increase particle velocity. In addition to accelerating the particles, such plates and fields can be used to manipulate the particle beam, making it more uniform.
[0113] Velocity enhancement can also be effected in the acceleration cells by using sloped walls inside the cells. This has been mentioned previously in the discussion of FIGS. 5A-6B and will be expanded upon below in a discussion of FIGS. 7A-9B.
[0114] Yet another method for increasing the velocity of the charged resin particles includes altering the geometry of the Venturi constriction, particularly its slope on the wide aperture side of the constriction. Increasing the size of the powder inlets near the Venturi constriction, or using inlets of different sizes, also can increase the velocity of the charged particles.
[0115] Reference is now made to FIGS. 7A-7C where three schematic views of a nozzle 23 of an acceleration cell 12 are shown. Nozzle 23 represents the end of an acceleration cell closest to the coating chamber. Nozzle 23 shown in FIGS. 7A-7C can be used with both the high-voltage and friction-charging type acceleration cells discussed above. The nozzle shown enhances particle beam uniformity and increases the velocity of the particles.
[0116] A top-side schematic cut-away view of nozzle 23 of an acceleration cell constructed and operative according to the present invention is shown in FIG. 7A. Nozzle 23 contains four airflow control vanes 54 , which assist in controlling the spatial uniformity of the particle distribution. It is readily understood that more or less than four vanes can also be present. Vanes 54 can be constructed of any suitable plastic.
[0117] In the embodiment of the present invention shown in FIGS. 7A-7C, nozzle 23 is constructed so that there are slopes (S 1 and S 2 ) in two dimensions of the nozzle. This can best be seen in FIGS. 7B and 7C which are schematic top and side views respectively of nozzle 23 . In yet other embodiments, a slope can be present in only a single dimension, such as the one shown in FIG. 7C, with a slope absent from the dimension best seen in FIG. 7B. In still other embodiments, shown in FIGS. 5A-6B, in addition to slopes S 1 and S 2 of nozzle 23 , acceleration cell 12 also contains slopes S 3 and S 4 extending back into the acceleration cell, almost reaching Venturi constriction 22 or mixing region 27 , the latter to be discussed below.
[0118] The slope of acceleration cell 12 from wide aperture 46 to mixing region 27 or Venturi constriction 22 does not need to be a constant. As best illustrated in FIGS. 5A and 6A, the slope can be less in the stabilization region 29 extending from the mixing region 27 to nozzle 23 and greater in the region of nozzle 23 . Including a slope in the part of acceleration cell 12 closest to aperture 46 increases the uniformity of the charged particle distribution and accelerates the particles as they approach and exit aperture 46 . Typically, the angle of slopes S 1 and S 2 in the region of nozzle 23 can range up to about 40 degrees, preferably up to about 15 degrees and even more preferably up to 10 degrees.
[0119] In the above discussion and Figures, we have used S 1 -S 4 as the four possible slopes of the various regions of the acceleration cell. The use of different designations 1 - 4 for the four slopes does not necessarily imply that they are all different. In some embodiments, some, or all, of the slopes may be identical.
[0120] Reference is now made to FIG. 8 where a cut-away, top-side view of the region between the Venturi constriction 22 and the wide aperture 46 of a typical acceleration cell, constructed and operative according to a preferred embodiment of the present invention, is shown. This part of the cell includes several regions: a Venturi constriction 22 , a mixing region 27 , a stabilization region 29 and a nozzle region 23 . Nozzle region 23 has been discussed above with respect to FIGS. 7A, 7B and 7 C. Similarly, the Venturi constriction 22 has been discussed elsewhere. Mixing region 27 is meant to increase the uniformity of the charged particle distribution, while stabilization region 29 is intended to stabilize the flow as the particles approach nozzle region 23 where they are further accelerated by an increasingly sloped internal wall and a constantly decreasing cross-sectional area.
[0121] Mixing region 27 can be constructed as shown in FIGS. 9A, 9B and 9 C to which reference is now made. In the embodiment shown, deflectors 53 introduce turbulence into the moving air and charged particles after they have traversed the Venturi constriction. This turbulence increases the uniformity of the particle distribution as the particles approach the nozzle region. As shown in FIGS. 9B and 9C, the orientation of deflectors 53 , attached to the bottom of the cell, are typically opposite to that of deflectors 531 , positioned on top of the cell. FIGS. 9B and 9C show top views of turbulence-inducing deflectors 53 and 53 ′, and their opposing displacements are clearly observable. In FIGS. 9A, 9B and 9 C, deflectors 53 and 53 ′ are mounted on bases 51 and 51 ′ respectively.
[0122] It should be readily apparent to those skilled in the art that the number of deflectors can be more or less than that shown in the figures, the number being determined by the degree of agitation required for charged particle uniformity. It should further be apparent to one skilled in the art that turbulence-inducing elements of any shape, or the use of any turbulence-producing means, can be used as long as they produce a satisfactorily uniform particle distribution in the particle discharge stream. Moreover, any means—turbulence-producing or otherwise—that produces satisfactory uniformity in the particle distribution of the discharge stream can be used. One such means for improving uniformity would be the insertion of a plastic screen in the nozzle region of the acceleration cell. The screen would include a mesh large enough to prevent clogging and small enough to improve discharge stream uniformity.
[0123] In embodiments of the present invention, the size of the aperture, that is its length and width, and the angle at which the projected charged powder impinges on the substrate, can be adjusted to produce a powder coating of a desired thickness and uniformity. Therefore, further embodiments of the present invention provide for acceleration cells in which the apertures are mechanically variable apertures. In these embodiments, the size of the aperture and/or the angle between the plane containing the wide aperture and a plane, or a “virtual” plane, of the substrate being coated can be varied. The “virtual” plane here refers to instances when the substrate is not necessarily planar; the plane then being coated is a “virtual” plane, which constitutes the surface being coated projected onto a plane.
[0124] Alternatively, the aperture region of the cell can be enclosed in a detachable structure, the structure being replaceable with any of a series of similar structures, each such structure having an aperture of different dimensions, angle of incidence and/or shape. Depending on coating needs, the shapes of these structures can include conical structures such as those in FIG. 5A-6B, straight structures such as in FIGS. 3-4B and even round or rectangular horn-shaped structures similar to those found on loudspeakers.
[0125] It is readily apparent that the uniformity of the coating depends on the uniformity of the particle beam emitted from the aperture. Preferably, the beam should be as narrow as possible when emerging from the cell. Accordingly, increasing the cell's aperture aspect ratio, that is the ratio of the aperture's length to width (or equivalently the ratio of its larger to its shorter dimension) and/or decreasing the aperture's cross-sectional area, typically enhances the uniformity of the particle discharge stream.
[0126] Particle size also affects coating uniformity. Small particles of five microns or less have a greater surface area to volume ratio than larger particles. This results in a larger electrical charge to volume ratio, which increases particle velocity and enhances particle penetration of the substrate, leading to a more uniform coating and smaller resin loads. The fibers in composite substrates generally have a thickness of 5 to 20 microns and the inter-fiber spacings of such substrates are generally even smaller. As a result, it is readily apparent that particles of less than 5 microns can penetrate the spaces between such fibers more easily than conventional 50-100 micron resin particles. In addition, small micron-size particles, because of their high kinetic energy, can separate the fibers of the substrate. Finally, in addition to the penetration capability of small particles, they also charge more easily because of their greater surface area to volume ratio; accordingly, charging voltage can be reduced. As has been mentioned previously, recent improvements in the fabrication of micron-size resin particles will make the use of such small particles more commonplace. Mixed electrical/friction-charging cells or the concurrent use of both frictional and electrical charging cells in a single system as discussed above, will assist in assimilating such particles in prepreg manufacture.
[0127] It should be appreciated that two-stage coating would be particularly advantageous when using small particles. The first stage of coating would employ small (5 microns or less) particles and would ensure good penetration of the substrate and thus better uniformity. In the second stage of coating, larger size resin particles would be deposited; this would lead to a faster overall deposition rate and reduce the time needed to coat a unit length of substrate.
[0128] As can readily be concluded from the discussion above, achieving a uniform coating requires control of many variables. This includes controlling the charging voltage, air blower speed, pressure differential at the Venturi constriction and the amount of powdered resin carried per unit volume of airflow. Additional factors, which enter into the quality and uniformity of the coating, are the type, weave, fiber diameter and conductivity of the substrate. Additionally, the speed at which the substrate moves, the amount of powder used, the size distribution and density of the powder, the sizing used on the substrate, and the degree of ionization in the region of the substrate are important. The latter factor depends on charging voltage, humidity in the region of charging and the amount of charge lost in transit. Theoretically, as many of the above factors as possible should be monitored and, when necessary, adjusted to obtain an optimal coating.
[0129] A computerized control system can be used with embodiments of the present invention. Variables such as air blower speed, substrate velocity, charging voltage, output voltage and output current can be measured by various sensors and transferred to a data acquisition unit, which is part of the computer used to control the coater system. The computer can include additional interface provisions for controlling the coater's active elements (high-voltage power source, air blowers, substrate conveyor, etc.). One typical interface architecture that could be used includes a general purpose interface bus (GPIB). At the direction of the computer, the output of the active elements can be adjusted via the interface to provide the charging voltage, air blower speed, substrate velocity, etc. that optimizes the coating.
[0130] Prior to any control system being fully operational, data is gathered about as many of the key variables discussed above as possible, and a regression analysis for optimizing the coating is performed. This analysis and data are stored in the computer and used to analyze the values sensed by the above-mentioned sensors. Based on a comparison of the computer's stored data, regression analysis and the sensed data, the computer communicates, via the interface, to the active elements of the system the values required to optimize the coating.
[0131] The definitions given above have been adhered to while discussing the construction and operation of the present invention. However, it should be readily apparent that the above-described invention can be applied to other substrates whenever a uniform, low load coating is required. These substrates need not necessarily be substrates used in forming prepregs for use in fabricating composites. Without being limiting, these substrates can include solid substrates such as metal, wood and Formica®, among others. Furthermore, the substrates defined hereinabove, which inter alia include carbon fibers, fabrics, tow and strands can also include tapes and tubes, particularly carbon tapes and tubes.
[0132] It will be appreciated by persons skilled in the art that the present invention is not limited by what has been particularly shown and described hereinabove. Rather the scope of the invention is defined by the claims that follow. | An acceleration cell for use in coating substrates with plastic resin particles. The cell includes a housing that has an air inlet port, an air outlet port, and a particle feed port, the latter in association with a resin particle source. The housing receives a carrier airflow for taking up resin particles so that the particles are suspended in the carrier flow. The air outlet port has a configuration having a predetermined width, which generally corresponds to the width of the substrate. The cell also contains at least one electrostatic charger for charging the suspended resin particles and at least one apparatus for accelerating the carrier flow and the suspended particles. Finally, the cell includes at least one flow-modifying apparatus for modifying the resin particle outflow, producing a uniform delivery of the particles across the substrate. | 1 |
BACKGROUND OF THE INVENTION
This invention relates to a multiple valve engine and more particularly to an improved induction system for an internal combustion engine having multiple intake valves.
It is well known that the specific output of an internal combustion engine can be increased by using two or more intake valves for each combustion engine rather than the more conventional single intake valve. The use of multiple intake valves provides a greater valve opening area than with a single valve and also permits higher running speed due to the lower inertia of the multiple, but smaller valves. Thus, it is common practice to employ two or sometimes even three intake valves per chamber for high performance engines.
The advantages of multiple intake valves can also be enjoyed with more conventional power plants such as those utilized to propel normal automobiles or motorcyles of other than the high performance type. However, the use of multiple intake valves of the type previously proposed tends to provide extremely poor running under slow speed conditions. The reason for this is that the gas velocity through the induction tract is very slow at low engine speeds and fuel has a tendency to condense on the induction passages and within the combustion chamber. In addition, the flow of the intake charge into the combustion chamber is very sluggish and this results in very slow flame travel and incomplete combustion.
It is, therefore, a principal object of this invention to provide an improved induction system for an internal combustion engine that will improve its performance throughout the entire engine load and speed ranges.
It is another object of this invention to provide an induction system for a multiple intake valve engine that provides good running characteristics at low speeds.
SUMMARY OF THE INVENTION
This invention is adapted to be embodied in an induction system for an internal combustion engine comprising a variable volume chamber, a first intake passage communicating with the chamber through a first intake port and a second intake passage communicating with the chamber through second and third intake ports. In accordance with the invention, the first intake passage has a substantially smaller effective cross-sectional area than the second intake passage.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a partially schematic view of a portion of an internal combustion engine having an induction system constructed in accordance with an embodiment of the invention.
FIG. 2 is a cross-sectional view taken through the engine on a plane containing the axis of the cylinder bore.
FIG. 3 is a bottom plan view showing the lower face of the cylinder head and is taken generally along the line 3--3 of FIG. 2.
FIG. 4 is a cross-sectional view taken along the line 4--4 of FIG. 3.
FIG. 5 is a cross-sectional view taken along the line 5--5 of FIG. 3.
FIG. 6 is a schematic top plan view showing the configuration of the intake and exhaust passages.
FIG. 7 is a side elevational view of a portion of one of the intake passages.
FIG. 8 is a slide elevational view of another portion of that one intake passage.
FIG. 9 is a side elevational view of the other of the intake passages.
FIG. 10 is a typical side elevational view of one of the exhaust passages.
FIG. 11 is a series of cross-sectional views taken along the lines E0 through E6 of FIG. 6 and 7.
FIG. 12 is a series of cross-sectional views taken along the lines E7 through E10 of Figures and 8.
FIG. 13 is a series of cross-sectional views taken along the lines E11 through 16 of FIGS. 6 and 9.
FIG. 14 is a series of cross-sectional views taken along the lines A0 through A4 of FIGS. 6 and 10.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
An internal combustion engine having an induction system constructed in accordance with an embodiment of the invention is identified generally by the reference numeral 11. Inasmuch as the invention relates primarily to the induction system for the engine 11, only this portion of the engine has been illustrated and will be described in detail. Also, for the same reason, only a single cylinder has been illustrated and will be described. It should be understood, however, that the invention is capable of use in engines having multiple cylinders and any type of cylinder configuration.
The engine 11 includes a cylinder block 12 having a cylinder bore 13 in which a piston (not shown) reciprocates and which is connected by means of a connecting rod (not shown) to a crankshaft for driving the crankshaft in a known manner.
A cylinder head 14 is affixed to the cylinder block 12 in a known manner and is provided with a chamber 15 that cooperates with the cylinder bore 13 and piston so as to provide a chamber of volume which cyclically varies and which will at times hereinafter be referred to as the combustion chamber. A primary induction passage, indicated generally by the reference numeral 16 is formed both in the cylinder head 14 and in an associated intake manifold, which appears only in a schedmatic fashion in FIG. 1, and which terminates at an intake port in the cavity 15. This intake port is defined by a value seat 17. A first intake valve 18 is supported for reciprocation by the cylinder head assembly 14 in a known manner and controls the flow through the primary intake passage 16 into the combustion chamber 15.
The cylinder head 14 and associated intake manifold is provided with a secondary induction passage 19 that has a single entrance opening 21 formed in the outer face of the cylinder head 14 and which branches into two portions 22 and 23 each of which terminates in a respective intake port defined by valve seats 24 and 25. Intake valves 26 and 27 are supported by the cylinder head assembly 14 and control the flow through the secondary induction passage 19 and the respective intake ports defined by the valve seats 24 and 25.
Each of the intake valves 18, 26 and 27 is operated by means of an overhead mounted camshaft 28 that has lobes 29 that cooperate with finger followers 31 for actuating the intake valves 18, 26 and 27 simultaneously. Alternatively, the intake valves 18 and 26 and 27 may be operated in a stages sequence.
The primary intake passage 16 is provided with a charge former in the form of a piston type carburetor 32 of a known type. The carburetor 32 has not been shown in full but only the throttle valve portions have been illustrated which includes a sliding piston 33 that is coupled to a metering needle that cooperates with a jet in the fuel bowl 34 of the carburetor 32 for controlling the fuel flow through the primary intake passage 16 in proportion to the effective size of the air opening provided by the position of the piston 33.
In a similar manner, a charge former 35 is provided for supplying a charge to the secondary induction passage 19. The charge former 35 may be of the known air valve carburetor type and includes a downstream manually operated throttle valve 36. Upstream there is provided a floating piston 37 that assumes a position so as to maintain a constant pressure drop across the induction passage 19. A metering rod affixed to the piston 37 cooperates with a metering jet in the fuel bowl 38 of the carburetor 37 for varying the fuel flow.
The position of the throttle valves comprising the piston 33 and butterfly type throttle valve 36 is controlled by a suitable staged accelerator mechanism. In the illustrated embodiment, the engine 11 is adapted to be embodied in a motorcycle and, for that reason, a hand throttle grip 41 is rotatably journaled on one of the handlebars. An accelerator cable 42 interconnects the throttle grip 41 with a drum 43 that is affixed to a throttle valve shaft 44 of the carburetor 32. This throttle valve shaft carries an actuating lever 45 that engages and operates the piston 33 so as to control its position.
Means including a lost motion connection are provided for connecting the throttle shaft 44 with a throttle valve shaft 46 to which the throttle valve 36 of the carburetor 35 is provided. This includes a drum or disk 47 that is affixed to the throttle shaft 44 and which carries an adjustable stop 48. The stop 48 is normally spaced from a lever 49 that is affixed to the shaft 46 when the engine 11 is in its idling condition. As the throttle valve 33 is progressively opened, a point will be reached when the adjustable stop 48 contacts the lever 49 and the throttle valve 36 will then be progressively opened. The reason for this will be explained now.
FIGS. 11, 12 and 13 show the size and configuration of the induction passages 16 and 19. FIGS. 11 and 12 show the induction passage 16 and its branch portions 22 and 23 while FIG. 13 shows the induction passage 19. The cross-sectional areas at sections taken along their length progressing from the inlet ends on the outer side of the cylinder head 14 to the inlet ports 17, 24 and 25 is shown in the direction of the arrow A. It will be noted that the primary intake passage 16 has a substantially smaller effective area at its inlet end than does the secondary induction passage 19. The passages 16 and 19 are configured, however, so that the inlet ports 17, 24 and 25 are all the same diameter so that the intake valves 18, 26 and 27 may all have the same diameter. This lends a greater simplicity to the engine construction and arrangement. However, due to the throttling arrangement of the staged throttle valves already described, when the engine is operating at idle and low speeds, the total effective induction area will be only that of the primary induction passage 16 and the small cross-sectional area will insure a high gas velocity in the induction passage 16 and into the combustion chamber 15 so as to insure good vaporization of the fuel and considerable turbulence in the combustion chamber 15 so as to promote rapid flame propagation.
As the throttle valve 36 begins to open, however, there will be increased flow through the induction passage 19 and into the chamber 15 through the intake valves 26 and 27 so that there will be good breathing and maximum power output can be achieved.
A spark plug opening 49 is formed centrally in the combustion chamber 16 to receive a spark plug with its gap at substantially the center of the combustion chamber 16. This is utilized to fire the charge within the combustion chamber 16 in a known manner.
It should be noted that the intake ports 17, 24 and 25 lie substantially on one side of a plane containing the axis of the cylinder bore 13 and spark plug 49. A pair of exhaust passages 51 and 52 are formed in the cylinder head 14 on the other side of this plane. The passages 51 and 52 terminate in respective exhaust ports that are defined by exhaust valve seats 53 and 54. Exhaust valves 55 and 56 are supported by the cylinder head 14 and control the flow through the exhaust ports 53 and 54 and exhaust passages 51 and 52. Like the intake valves 18, 26 and 27, the exhaust valves 55 and 56 are operated by means of an overhead mounted camshaft having lobes that engage finger followers 57 for operating these valves in a known manner.
As may be seen in FIG. 14, the exhaust passages 52 have a configuration that provides a substantially constant flow area throughout their length. The exhaust ports 53 and 54 are of the same diameter so that exhaust valves of the same size may be utilized.
It should be readily apparent from the foregoing description that an induction system has been described that provides extremely good running throughout the engine load and speed ranges and which is still capable of obtaining maximum power due to its large effective cross-sectional area. However, the use of the two induction passages of different sizes and the staged throttle valve arrangement, there will be good velocities and rapid combustion even at low speeds.
Although an embodiment of the invention has been illustrated and described, various changes and modifications may be made without departing from the spirit and scope of the invention, as defined by the appended claims. | An induction system for an internal combustion engine for improving running throughout the entire engine speed and load ranges. The induction system comprises a first intake passage that serves the chamber through a first intake port and a second intake passage that serves the chamber through second and third intake ports. The effective cross-sectional area of the first intake passage is substantially smaller than that of the second intake passage and staged throttle valves are incorporated so that the charge requirements at low speed are supplied primarily through the first intake passage. | 5 |
BACKGROUND OF THE INVENTION
The invention relates to tool couplers for excavation, demolition and construction equipment.
Some types of construction equipment, such as backhoes and excavators, have a movable dipperstick (also referred to as an arm) to which a variety of tools, such as, for example, buckets and grapples, can be attached. A hydraulic linkage allows the equipment operator to pivot the tool from the free end of the dipperstick. To simplify the process of changing tool attachments, a universal coupler can be fixed to the dipperstick linkage. A selected tool can then be removably attached to the coupler, a process that typically involves manually positioning at least one latch pin between the coupler and the tool.
There is a trend in the industry to use an actuated coupler on the end of the dipper stick for connecting and disconnecting a tool from the linkage. A great advantage of these systems is that the operator can actuate the coupler to connect or disconnect a tool without the assistance of another worker and without having to leave the cab of the vehicle.
One type of actuated coupler first engages a crossbar formed in the tool with hooks depending from the coupler, and then engages a latch pin (or a block or a wedge) with a mating receptacle formed in a collar on the tool. A double-action hydraulic cylinder in line with the latch pin is positioned so that the cylinder extends to push the latch pin into the receptacle. In disengaging the tool from the coupler, the operator retracts the rod into the cylinder body, pulling the pin out of the receptacle.
SUMMARY OF THE INVENTION
The invention provides a coupling assembly for coupling a tool to a dipperstick, or arm, on an apparatus which has a hydraulic system for moving the tool. The coupling assembly includes a coupler body having a frame that defines a central cavity, and also having link structure for pivotally coupling to the dipperstick. An actuator assembly positioned within the central cavity includes a latch pin movable between an extended position and a retracted position. In the extended position, an end of the latch pin projects rearward from an opening in a rear end of the frame for engaging an aperture or receptacle defined by the tool. In the retracted position, the end of the latch pin is disengaged from the tool receptacle and positioned substantially within the frame. The actuator assembly also includes a hydraulic latch cylinder that has a movable part, and a fixed part. The movable part is coupled to the latch pin by a latch pin coupling assembly, which is structured and arranged such that, when the movable part is extended from the fixed part, the latch pin moves to the retracted position.
According to another aspect of the invention, the latch pin coupling assembly includes a bias member structured and arranged to apply a bias force that urges the latch pin towards the extended position. When a threshold level of hydraulic pressure is applied to the latch cylinder, the movable part of the cylinder overcomes the bias force and extends to move the latch pin to the retracted position and out of engagement with the tool.
Another feature of the invention is that the latch cylinder can be a single-action cylinder.
According to another feature of the invention, the latch cylinder can be positioned on an axis different from an axis defined by the latch pin, such as along side the latch pin. This feature provides a compact arrangement. The system is easily adaptable to any type of quick coupler type system due to the compactness and placement of the actuating cylinder.
According to another feature of the invention, the hydraulic pressure to the latch cylinder can be controlled by an electrically actuated valve assembly that hydraulically couples the dipperstick hydraulics to the latch cylinder. The valve assembly can include one or more solenoid valves that only allow hydraulic pressure to enter and remain in the latch cylinder when they are energized.
According to another feature of the invention, the valve assembly can be structured and arranged such that the dipperstick hydraulics must be approximately fully pressurized while extended to pressurize the latch cylinder.
According to another feature of the invention, the coupling assembly can also include a pin indicator that readily shows whether the latch pin retracted. The indicator is located such that it can be viewed easily from the operator position.
According to another feature of the invention, a drop in hydraulic pressure in the latch cylinder below the threshold level allows the bias spring to push the coupling pin towards the extended position. An unexpected hydraulic pressure loss can be caused by a failure in the hydraulic system or by a failure in the valve assembly. The spring apply, hydraulic release system is safe in that it assures that an attached tool will not accidentally uncouple from the coupling assembly if there is a loss in hydraulic pressure in the latch cylinder.
The invention also provides a method of removing a tool from the coupler assembly having features as described above. An operator can remove a tool by the steps of applying hydraulic pressure to a latch cylinder that has a part fixed relative to the coupler body and a movable part rigidly coupled to the latch pin, extending the movable part from the fixed part, thereby urging the latch pin to the retracted position, engaging a cross member of the excavation tool with a hook structure depending and extending forward from the coupler body, rotating the coupler body toward the tool, aligning the latch pin with a mating receptacle formed in the excavation tool, reducing hydraulic pressure to the latch cylinder, and applying a bias force to the latch pin, urging the latch pin to the engaged position, thereby engaging the latch pin in the receptacle and securing the excavation tool to the coupler body.
According to another aspect of the invention, the method further includes the step of removing the tool from the coupler, including rotating the coupler body and the tool to a full forward position, again applying hydraulic pressure to the latch cylinder, again extending the movable part from the fixed part, thereby urging the latch pin to the retracted position and disengaging the latch pin from the receptacle, and disengaging the hook structure from the cross member of the excavation tool.
The latch cylinder extends using the more powerful head end to extract the latch pin, whereas coupling systems using an in-line dual-action cylinder and latch pin arrangement use the less powerful rod end for this purpose. This feature of the invention is important when extracting a frozen pin, which can require substantially more force than inserting a free moving pin.
Since the hydraulic system uses a single-action latch cylinder, it only requires one hydraulic line between the valve assembly and the latch cylinder. This is simple and inexpensive compared with coupling systems that use a dual-action cylinder, and that require two hydraulic connections.
The rod of the latch cylinder is normally in the retracted position during the tool working period. Because the latch cylinder is retracted, the rod of the latch cylinder is not subject to damage from rocks and sharp objects. Normally, the only time the rod is extended, and thereby exposed to the elements and contaminants, is when a tool is being attached or detached from the coupling assembly.
A feature of the invention is that if there is a loss of either electrical or hydraulic power, the latch pin will extend or "insert" automatically. If electrical power inadvertently gets to the solenoid valves, the tool has to be fully rolled forward and inward in order for the pressure to build up in the latch cylinder to retract latch pin. In this position, the coupler hooks are fully engaged and the likelihood of the tool falling off is minimized. One cannot simply throw the switch and have the tool fall to the ground.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a perspective view of dipperstick with an attached coupling assembly, and a conventional bucket that can be attached to the coupling assembly.
FIG. 2 is a side view of a hydraulic coupling assembly shown coupling a conventional bucket to a dipperstick.
FIG. 3 is a top plan view of a coupling assembly, partially showing a bucket, with the latch pin in an unlatched, retracted position. FIG. 3A is a similar view, partially broken away, showing the latch pin in a latched, extended position.
FIG. 4 is a section view through line 4--4 of FIG. 3. FIG. 4A is a similar section view through line 4A--4A of FIG. 3A.
FIG. 5 is a partial section view through line 5--5 of FIG. 3. FIG. 5A is a similar partial section view through line 5A--5A of FIG. 3A.
FIG. 6 is a schematic diagram of a hydraulic system and an electrical system according to the invention. FIGS. 6A, 6B and 6C illustrate other embodiments of a valve assembly.
In the following detailed description of the invention, similar structures that are illustrated in different figures will be referred to with the same reference numerals.
It will also be noted that the figures are generally not drawn to scale.
DETAILED DESCRIPTION OF THE INVENTION
Referring first to FIGS. 1 and 2, a hydraulic coupler assembly 10 according to the invention is attached to a conventional dipperstick or arm 12. Only a free end of dipperstick 12 is illustrated in FIGS. 1 and 2. The other end of dipperstick 12 is pivotally coupled, typically via an intermediate articulation (not shown), to a base (not shown) that includes a hydraulic power system, and hydraulic and electric operator controls located in a cab. Coupler assembly 10 can be used for coupling the dipperstick 12 to any of a variety of tools, such as, for example, a conventional bucket 14.
Dipperstick 12 linkage includes a bucket guide link 16 pivotally attached to the dipperstick 12, a bucket cylinder 18 for actuating the coupling assembly 10 and the bucket 14, and a bucket link 20. Extending bucket cylinder 18 rotates coupling assembly 10, and any tool attached to coupling assembly 10, inwardly in a forward direction.
Referring now also to FIGS. 3-5, coupling assembly 10 includes a frame 24 forming a central space 22. Frame 24 includes side walls 26, a bottom plate 28, a coupler spreader plate 30 and a rear face plate 32. Depending from side walls 26 are a pair of forward extending hooks 34 that are adapted to fit through an opening or recess 36 formed in a back sheet 38 of bucket 14 (see FIG. 1). The hooks 34 can then engage a cross tube 40 to support a forward end of bucket 14.
Coupling assembly 10 has a pair of dipper pivot fixtures 42, located near a forward end of side walls 26 for coupling to dipperstick 12. A pair of link pivot fixtures 44 for coupling to bucket link 20 are located closer to the rear end of the frame 26. A pair of link pivot fixtures 46 are also provided at an alternate location.
Bucket 14 is adapted to be coupled to dipperstick 12 with coupling assembly 10. As noted above, a recess 36 is formed in back sheet 38 of bucket for receiving hooks 34. Once cross tube 40 is engaged by hooks 34, the bucket can be lifted off the ground by raising the dipperstick 12. This connection provides a first point of connection between coupling assembly 10 and bucket 14. To enable the bucket 14 to rotate by operation of the bucket hydraulic cylinder 18, a receptacle 50 formed in a latch collar 51 fixed to a plate 52 on the rear end of bucket 14 engages one end of a movable latch pin 48.
Latch pin 48 slides within the bore of a bushing 60 welded to rear face plate 32 within frame 24. On the other side of plate 32 there is an approximately semicircular-shaped coupler crescent 61 that fits over the top of latch collar 51 when bucket 14 is attached to coupling assembly 10.
The latch pin 48 is part of an actuator assembly 54 that also includes a coil spring 56, or other type of compression spring, for pushing the latch pin 48 through bushing 60 into engagement with the receptacle 50, and a single-action latch pin hydraulic cylinder 58 that acts opposite the spring 56 to disengage the latch pin 48 from the receptacle 50. Spring 56 is positioned approximately in line with latch pin 48, and latch cylinder 58 is positioned on a parallel axis along side latch pin 48 and spring 56. This arrangement allows the cylinder 58 to "push" the pin 48 out to retract. The spring 56 urges the pin 48 toward an engaged position with receptacle 50 when hydraulic pressure in the latch cylinder 58 is insufficient to overcome the spring force of spring 56. The latch pin 48 is normally in the engaged position because latch cylinder 58 is normally not pressurized.
Coil spring 56 is kept in position by a latch spring assembly that forms part of actuator assembly 54. One end of coil spring 56 bears against a pin block 62 that is welded to latch pin 48. Pin block 62 includes an annular groove to receive coil spring 56. The other end of coil spring 56, towards the front of coupler 10, bears against a winged end plate 64 and thereby holds the winged end plate 64 within the "V" formed by coupler spreader plate 30. A spring guide rod 66 is positioned within the coils of spring 56. Spring guide rod 66 extends transversely through a hole formed in end plate 64 and is welded thereto. A forward end of spring guide rod 66 includes a notch 68 that is positioned against an angled top edge 69 of coupler spreader plate 30 and held in place by the spring force from spring 56. The other end of spring guide rod 66 acts as a stop for latch pin 48 in the retracted position (see FIG. 4).
The body 70 of latch cylinder 58 is fixed to pin block 62. In the embodiment illustrated in FIGS. 3-5, body 70 has screw threads formed on its outer surface and screws into mating threads formed in a through hole in pin block 62, and is held in place by a set screw 71. The cylinder's extensible rod, or piston 72, extends through the hole in pin block 62. When hydraulic pressure coupled into cylinder 58 through hydraulic fitting 73 is increased, cylinder 58 extends and the free end of piston 72 bears against push plate 74, which is welded to bushing 60.
Extension of cylinder 58 with sufficient force to overcome spring's 56 spring force thereby urges latch pin 48 to a retracted position since latch pin 48 is welded to pin block 62 and pin block 62 is fixed to cylinder body 70. Release of pressure in cylinder 58 allows spring 56 to extend, urging pin block 62, and thereby latch pin 48, toward a latched position wherein the latch pin 48 projects beyond rear face plate 32.
Pin block 62 includes a cylindrical opening 76 that receives spring guide rod 66 when latch pin 48 is retracted by actuation of cylinder 58 (see FIG. 3). As mentioned above, spring guide rod 66 stops latch pin 48 from retracting beyond a predetermined point. When latch pin 48 is fully retracted, the end of spring guide rod 66 is inside the cylindrical opening 76 in pin block 62 and projects beyond the corresponding end of spring 56. In this position, a transverse assembly hole 78 formed in the end of spring guide rod 66 is aligned with a U-shaped slot 80 formed in pin block 66. An assembly pin (not shown) can be placed in assembly hole 78. When pressure in cylinder 58 is released, latch pin 48 can be manually moved to the latched position, thereby releasing spring guide rod 66 from cylindrical opening 76 in pin block 62. Assembly pin in hole 78 keeps spring 56 compressed on spring guide rod 66. With pin block 62 out of the way, the assembled latch spring assembly, comprised of spring guide rod 66, spring 56, and winged end plate 64, can be removed as a unit from coupler 10. The latch spring assembly can be installed in coupler 10 by a reverse procedure.
Coupler 10 is structured to allow an operator in the control cab of the construction equipment to visibly assess whether the latch pin 48 is in the latched or retracted position, even when a tool is attached to coupler 10. Back sheet 38 of bucket 14 extends forward only to the attachment point of hooks 34, which leaves the forward portion of bucket 14 open between back sheet 38 and cross tube 40. Bottom plate 28 of frame 24 forms a U-shaped indicator slot 82 positioned between hooks 34. Indicator slot 82 is positioned such that pin block 62 is visible through the opening in bucket 14 and through indicator slot 82 when latch pin 48 is in the retracted position. When latch pin 48 is in the latched position, the operator's line of sight to pin block 62 is blocked by back sheet 38. Pin block 62 can be made more noticeable by painting it a bright color.
Referring now also to FIG. 6, a hydraulic circuit 86 for operating latch cylinder 58 taps into the hydraulics of the excavator. A hydraulic pump 88 and a reservoir 90 are coupled to bucket cylinder 18 via a lever-operated, three-position, two-pole valve 92. Pump 88, reservoir 90 and valve 92 are located in the base 93 of the excavator. Hydraulic hoses 94, 96 connect between valve 92 and the rod end 98 and cylinder end 100 of bucket cylinder, respectively. Hydraulic hose 96 has a T-connection leading to one port of a valve assembly 102. The T-connection can be conveniently made at the hydraulic fitting for the cylinder side 100 of bucket cylinder 18. The other port of valve assembly 102 connects via hydraulic hose 104 to fitting 73 in latch cylinder 58. Valve assembly 102 can be strapped, bolted or otherwise attached to a fixed part of bucket cylinder 18 or to an upper portion of dipperstick 12.
Valve assembly 102 includes two solenoid actuated valves 108, 110, each with a power connection controlled by a locking electrical toggle switch 111 located in the cab of the excavator. In an unlatch switch position the solenoids are energized and in a latch switch position the solenoids are shut off. When the solenoids are not energized (see FIG. 6), springs 112, 114 urge valves 108, 110, respectively to a position wherein a check valve portion 116 of valve 108 and a through portion 118 of valve 110 are connected in series between lines 96 and 104. When valves 108, 110 are energized (not shown), a through portion 120 of valve 108 and a check valve 122 portion of valve 110 are placed in the circuit.
Check valve 116 blocks a hydraulic flow from bucket cylinder 18 to latch cylinder 58, but is set to permit flow in the other direction when there is an over-pressure condition in the latch cylinder 58 relative to the cylinder side 100 of bucket cylinder 18. Check valve 122, on the other hand, blocks any back flow from latch cylinder 58 to bucket cylinder 18, and is set to permit the latch cylinder 58 to be pressurized when the cylinder side 100 of bucket cylinder 18 is fully pressurized. With the cylinder side 100 fully pressurized, bucket cylinder 18 will be fully extended and the coupling assembly 10 will be rotated fully forward.
Referring now to FIG. 6A, another embodiment of a valve assembly 102' includes valve 108 in series with check valve 124 between lines 96 and 104. Check valve 24 prevents back flow from line 104 to 96. A drain line 126 normally connects between line 104 and reservoir 90 via through portion 128 of solenoid valve 130. When valves 108 and 130 are energized, drain line 126 is blocked by check valve portion 132 of valve 130, and through portion 120 is positioned in series connection with check valve 124 between lines 96 and 104. Check valve 124, similar to check valve portion 122, is set to permit pressurization of line 104 and latch cylinder 58 when full hydraulic pressure is applied to extend bucket cylinder 18.
Referring to FIG. 6B, in a third embodiment, valve assembly 102" is configured with solenoid valves 108 and 110, similar to the arrangement of valve assembly 102. In addition, a drain line 134 connects between valves 108 and 110. Flow through drain line 134 to reservoir 90 is limited by an orifice 136 flow limiter.
Referring now to FIG. 6C, a fourth embodiment of a valve assembly 102'" includes solenoid valves 136 and 110. In the normal, non-energized configuration shown in the drawing, cylinder 58 drains to reservoir 90 via through portion 118 of valve 110 and lower through portion 140 of valve 138. When valves 110, 138 are energized, pressure line 96 is coupled to cylinder 58 via upper through portion 142 of valve 138 and check valve portion 122 of valve 110.
Valve assemblies 102', 102" and 102'" can be safer than valve assembly 102, especially in high back pressure systems, because of the drain connections to reservoir 90, however, the drain connections require an additional hydraulic hose.
Referring again to FIG. 6, indicator lights 148 and an audible indicator 144, such as a beeper sound device, located in the cab alert the operator that the switch 111 is in the energized, unlatch position. A warning lamp 146 mounted on the dipperstick 12 lights or flashes to help to alert surrounding personnel that the switch 111 is in the unlatch mode and that the latch pin 48 could be retracted. Of course, audible indicator 144 can be configured to be audible outside the operator cab.
A single operator in the cab of the excavation equipment can detach a tool, such as bucket 14, to the coupling assembly 10 and attach a new tool to the coupling assembly without any assistance, as described in detail below. Some particulars of the following recitation of steps for coupling and removing a tool are made with reference to the embodiment of valve assembly 102 illustrated in FIG. 6. It will be understood that the embodiments of valve assemblies 102', 102", and 102'" illustrated in FIGS. 6A, 6B, and 6C, respectively, will function in much the same manner, and the operator will make essentially the same sequence of steps to attach or detach a tool.
To decouple a tool from coupling assembly 10, the latch pin 48 must be moved to the retracted position. The operator first throws switch 111 in the cab to the unlatch position. The indicator lamps 148 and warning lamps 146 then light up, and the audible indicator 144 sounds. The solenoids becomes energized, which moves solenoid valves 108, 110 in valve assembly 102 to their unlatch position. Check valve 116 is moved out of hydraulic circuit 89 and check valve 122 is moved into hydraulic circuit 89. This, by itself, is insufficient to retract latch pin 48. Check valve 122 is set to prevent passage of hydraulic fluid and thus prevent latch cylinder 58 from being pressurized until the pressure on the cylinder side 100 of bucket cylinder 18 is greater than a predetermined value.
In the illustrated embodiments, check valve 122 is set such that the coupling assembly 10 and attached tool 14 must be rotated fully forward and approximately full pressure must be applied in line 96 to bucket cylinder 18 to open check valve 122. This assures that accidentally throwing switch 111 will not, by itself, be sufficient to retract latch pin 48.
Once the pressure in latch cylinder 58 is great enough to overcome the spring force of spring 56, latch cylinder 58 extends and thereby retracts latch pin 48. The operator can confirm that the latch pin 48 is retracted if he sees the pin block 62 in the retracted position. While the switch 111 is still in the "unlatch" position, the latch pin 48 will be held back retracted.
Alternatively, to bring the latch pin 48 to the retracted position, the operator can first rotate coupling assembly 10 forward, fully pressurize bucket cylinder 18, and then throw switch 111 to the unlatch position.
At this point, solenoid valves 108, 110 are still energized and in the unlatch position, and check valve 122 retains pressure in latch cylinder 58. The operator can then use free hands to maneuver the vehicle to disengage the hooks 34 from cross member 40 to uncouple the tool.
If the equipment is to remain idle for a period of time, the operator throws toggle switch 111 to the latch position, de-energizing the solenoid valves in valve assembly 102, and lowers hydraulic pressure in line 96. This allows pressure to drop in latch cylinder 58 such that spring 56 urges latch pin 48 to the engaged, or latched position, thereby bringing the piston 72 of cylinder 58 to a protected position retracted into cylinder body 70.
To attach a new tool, with the latch pin 48 still in the retracted position and the valves in the valve assembly 102 still energized, the operator adjusts pressure in the bucket cylinder 18 and maneuvers the coupling assembly 10 to insert hooks 34 into the recess 36 of the new tool and engage cross tube 40. The operator then lifts the tool off the ground, and rolls coupling assembly 10 forward by extending bucket cylinder 18. Coupler crescent 61 engages an upper side of latch collar 51, thus bringing latch pin 48 into alignment with receptacle 50 on bucket 14. The operator knows that the coupler crescent 61 has engaged latch collar 51 when he sees the bucket 14 visibly begins to roll forward. Less than full pressurization of the bucket cylinder 18 is typically required to bring the coupling assembly to this position.
The operator then throws switch 111 to the latch position. This de-energizes solenoid valves 108, 110 and moves check valve 122 out of hydraulic circuit 86 and check valve 116 into hydraulic circuit 86. Check valve 116 is set to open at a low differential pressure, such that hydraulic pressure will be released from the latch cylinder 58 when the back pressure in bucket cylinder 18 is much less than full pressure but great enough to rotate coupling assembly forward so that the coupling crescent engages the tool latch collar 50.
When the hydraulic pressure in latch cylinder 58 is released, spring 56 moves latch pin 48 into the engaged position with receptacle 50. The position of pin block 62 gives the operator a visible signal that the pin 48 is latched and the tool secured. Check valve 116 thereafter prevents the latch pin assembly from being inadvertently pressurized.
Other embodiments of the invention are within the scope of the following claims. | The invention provides a coupling assembly for coupling a tool to a dipperstick, or arm, on an apparatus which has a hydraulic system for moving the tool. The coupling assembly includes a coupler body having a frame that defines a central cavity, and also having link structure for pivotally coupling to the dipperstick. An actuator assembly positioned within the central cavity includes a latch pin that can slide between an engaged position and a retracted position. In the engaged position, an end of the latch pin projects out from a rear end of the frame for engaging a receptacle defined by the tool. In the retracted position, the end of the latch pin does not project out from the frame. A bias structure normally urges the latch pin toward the engaged position with a bias force. A hydraulic latch cylinder has a fixed part and a movable part rigidly coupled to the latch pin such that, when the movable part is extended from the fixed part, the latch pin is urged to the retracted position. | 4 |
FIELD OF THE INVENTION
The present invention relates to a controlled release device which provides sustained or pulsatile delivery of pharmaceutically active substances for a predetermined period of time. This invention further relates to a process for the manufacture of such a device and pharmaceutical compositions including the same.
DESCRIPTION OF THE BACKGROUND
Different systems have been developed for the delivery of pharmaceutical agents. One such system operates by means of a complicated osmotic pumping mechanism which is expensive and often difficult to prepare. Also known are delivery devices made of matrices using hydrogels. These devices use one or more hydrogels either selected from uncrosslinked linear polymers or from crosslinked polymers. None use both types of polymers in a single device.
While these systems do act to deliver selected pharmaceuticals, they do not provide for controlled release of the pharmaceutical in a sustained or pulsatile mariner for a predetermined period of time. In devices using uncrosslinked polymers, viscosity is the rate controlling factor for drug release kinetics. In these systems a gelatinous layer is formed on the surface upon hydration. The thickness and durability of this gelatinous layer depends upon the concentration, as well as the molecular weight and viscosity of the polymer in the device. At higher concentrations the linear polymer chains entangle to a greater degree leading to virtual crosslinking and a stronger gel layer. Drug release is effected by the dissolution of the polymer and erosion of the gel layer. Hence the rate of erosion controls the release rate.
In the case of devices using covalently crosslinked polymers, the drug is trapped in a glassy core in the dry state. On contact with an aqueous medium the surface of the device is hydrated to form a gelatinous layer which is different from the gel layer seen in uncrosslinked linear polymers. The hydrogel formed by crosslinked polymers does not consist of entangled chains but discrete microgels made up of many polymer particles, called a crosslinked network, in which the drug is dispersed. Therefore drug is trapped in the hydrogel domains. These hydrogels are not water soluble and do not dissolve, thus erosion as seen in uncrosslinked linear polymers does not occur. Drug release is by the osmotic pressure generated within the fully hydrated hydrogel which works to break up the structure by sloughing off discrete pieces of the hydrogel. The hydrogels remain intact while drug continues to diffuse through the gel layer at uniform rate.
U.S. Pat. Nos. 3,845,770, 3,916,899, 4,016,880, 4,160,452 and 4,200,098 disclose such delivery systems as described above. However, none of these patents teach the use of both covalently, crosslinked and uncrosslinked linear polymers in combination in a single delivery device for the controlled or pulsatile delivery of pharmaceutically active agents thereby taking advantage of their unique but different properties and mechanism of drug release.
SUMMARY OF THE INVENTION
The present invention provides a unique and novel synergistic approach to the use of multiple and differing polymers for modulating drug delivery.
It is an object of the present invention to provide a controlled release device which delivers therapeutically effective amounts of pharmaceutically active agents for a predetermined period of time in a controlled, continuous or pulsatile manner in mammals, especially human beings.
In accordance with an aspect of the invention is a controlled release pharmaceutical delivery device which provides sustained or pulsatile delivery of a selected pharmaceutically active substance for a predetermined period of time, the device comprises;
about 1 to 80% by weight covalently crosslinked water insoluble, water-swellable polymers; and about 1 to 75% by weight uncrosslinked, linear water soluble polymers.
In accordance with another aspect of the present invention is a controlled release pharmaceutical delivery device which provides sustained or pulsatile delivery of a selected pharmaceutically active substance for a predetermined period of time, the device comprises;
about 1 to 60% by weight of hydroxyethylcellulose; about 1 to 75% by weight of hydroxypropylmethyl cellulose; about 1 to 60% by weight of ethylcellulose; about 1 to 80% by weight of at least one Carbopol® resin; about less than 10% by weight of talc; about less than 10% by weight of magnesium stearate; and about less than 95% by weight granulating and tableting aids.
In accordance with yet another aspect of the present invention is a method for making an extended release formulation of pharmaceutically active agents, the method comprises;
blending about 1 to 80% pharmaceutically active agent with about 1 to 80% by weight covalently crosslinked water insoluble, water swellable polymers, and about 1 to 75% by weight uncrosslinked, linear water soluble polymers.
In accordance with another aspect of the present invention is a method for making an extended release formulation of pharmaceutically active agents, the method comprises;
blending about 1 to 80% pharmaceutically active agent with about 1 to 70% by weight uncrosslinked, water soluble polymers to form a homogeneous blend; granulating said homogeneous blend with a granulating solution to form a wet mass of granules and kneading said wet mass; drying said wet granules to a loss on drying of about less than 5%; reducing said dried granules such that granule size is less than about 1400 microns; blending said milled granules with about 1 to 80% of a crosslinked polymer, about less than 5% of a glidant, and about less than 5% of a lubricant; and compressing the lubricated granules into tablets.
In accordance with yet another aspect of the present invention is a pharmaceutical composition which comprises;
about 1 to 80% by weight pharmaceutically active agent; about 1 to 80% by weight covalently crosslinked water insoluble water swellable polymers; and about 1 to 75% by weight uncrosslinked, linear water soluble polymers.
In accordance with yet another aspect of the present invention is a pharmaceutical composition which comprises:
about 1 to 80% pharmaceutically active agent; about 1 to 60% by weight of hydroxyethylcellulose; about 1 to 75% by weight of hydroxypropylmethyl cellulose; about 1 to 60% by weight of ethylcellulose; about 1 to 80% by weight of at least one Carbopol® resin; about less than 10% by weight of talc; about less than 10% by weight of magnesium stearate; and about less than 95% by weight granulating and tableting aids.
In a further aspect of this invention there is provided a method for delivering soluble or poorly soluble pharmaceutically active agents by deliberate manipulation of the composition and ratios of crosslinked and uncrosslinked polymers present in the device.
In yet another aspect of this invention the controlled release delivery device also has use in other applications in which the release of a substance is desired into an environment which eventually comes into contact with fluids.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The novel controlled delivery device of the present invention provides a composition and a process for the formulation of pharmaceutically active agents into sustained release matrix tablets. The present invention is simple to prepare and permits efficient and reproducible mass production of the device using conventional pharmaceutical and biochemistry techniques.
Uncrosslinked linear polymers suitable for use in the present invention are the cellulosics preferably hydroxyethyl cellulose (HEC), hydroxypropylmethyl cellulose, ethylcellulose and hydroxypropyl cellulose. Crosslinked polymer suitable for use in the present invention are polymers of acrylic acid crosslinked with polyalkenyl alcohols or divinyl glycol. For example, these include water-swellable, high-molecular-weight crosslinked homopolymers and copolymers of acrylic acid, most preferably Carbopol resins.
In the preferred form the sustained release device of the present invention is presented as a matrix tablet suitable for oral administration which is prepared by intimately blending about 1 to 80% of a selected pharmaceutically active agent(s) with about 1 to 60% of an uncrosslinked linear polymer such as hydroxyethylcellulose (preferably Natrosol® 25OHHX PHARM) and about 1 to 75% of another uncrosslinked polymer such as hydroxypropyhnethyl cellulose (preferably Methocel® premium grade type K100M CR) in a planetary or high shear mixer until a homogeneous mixture is formed. The homogeneous mixture is then granulated with a granulating solution (preferably isopropyl alcohol) in a planetary or high shear mixer. It is preferable to knead the resultant wet mass for 1-3 minutes after wet granulation. The wet granules are then dried in a fluid bed dryer or tray dryer to a loss on drying (LOD) of about <5%. Preferably, the granules are dried in a tray dryer at >40° C. to an LOD of about <2%.
The dried granules are size reduced in a mill, preferably a Cone mill, such that the resultant granule size is about <2000 microns. The milled granules are intimately blended with about 1 to 80% by weight of a crosslinked polymer such as Carbopol® resin, preferably Carbopol® 934 P NF or 971 P NF in a V-blender. The Carbopol® treated granules are then intimately blended with a glidant such as talc (about <5% by weight) in a V-blender. The talc treated granules are then intimately blended with a lubricant such as magnesium stearate (about <5% by weight) in a V-blender. Finally, compression of the lubricated granules is done using a rotary tablet press to form tablets suitable for oral administration. The resultant tablets have a hardness of about >3 Strong Cobb units and a friability of about <1%.
The device may contain up to 95% by weight other granulating or tableting aids such as silicone dioxide, lactose, microcrystalline cellulose, calcium phosphate and mannitol.
The conditions under which the materials are processed and the relative proportions of the several components produces a device and composition having unique sustained release characteristics. The sustained release characteristic of the composition can be predetermined and varied by adjusting the makeup of the composition within the aforesaid limits. The duration, uniformity and continuity of release of the pharmaceutically active agent(s) can be suitably controlled by varying the relative amount of the covalently crosslinked and uncrosslinked linear polymers.
The finished tablet may be film coated with about 0.5 to 50% by weight of a suitable film coating comprising anionic polymers based on methacrylic acid and methacrylic acid esters or neutral methacrylic acid esters with a small proportion of trimethylammonioethyl methacrylate chloride or cellulose esters.
The pharmaceutically active agents that may be used with the device and in the compositions of the present invention may include but are not limited to diltiazem, buspirone, tramadol, gabapentin, verapamil, etodolac, naproxen, diclofenac, COX2 inhibitors, budesonide, venlafaxine, metoprolol, carbidopa, levodopa, carbamazepine, ibuprofen, morphine, pseudoephedrine, paracetamol, cisapride, pilocarpine, to methylphenidine, nifedipine, nicardipine, felodipine, captropril, terfenadine, pentoxifylline, fenofibrate, flipizide, aciclovir, zidovudine, moclobemide, potassium chloride, lamotrigine, citalopram, cladribine, loratadine, pancrelipase, lithium carbonate, orphenadrine, ketoprofen, procainamide, ferrous sulfate, risperidone, clonazepam, nefazodone, lovastatin, simvastatin, pravachol, ketorolac, hydromorphone, ticlopidine, seligiline, alprazolam, divalproex or phenytoin.
When the delivery device of this invention is made as a composition containing a pharmaceutical agent and is administered to the gastrointestinal tract by the oral route, it comes into contact with an aqueous environment and hydrates forming a gelatinous layer. If the drug is poorly soluble it will partition into the hydrophobic domains of the device provided by the crosslinked polymer while some will be entrapped in the hydrophilic matrix provided especially by the uncrosslinked polymer. This results in dependency √{square root over (t)}(Fickian) and zero order (case II) drug dissolution kinetics. For water soluble drugs, Fickian drug release kinetics will occur due to fast dissolution of the drug through the water filled interstitial spaces between microgels of the crosslinked polymer and dissolution and erosion of the uncrosslinked polymer. The presence of the crosslinked polymer, which does not dissolve, helps to maintain the integrity of the swollen gel structure that results. The mechanism or mechanisms that dominate will depend upon the ratio of crosslinked and uncrosslinked polymers present in the device which in turn impacts on the macro- and microviscosities of the gel layer. Thus, manipulation of the ratios of uncrosslinked and crosslinked polymers, results either in the controlled, sustained release or pulsatile release of the pharmaceutical contained therein.
EXAMPLES
The examples are described for the purposes of illustration and are not intended to limit the scope of the invention.
Methods of chemistry, biochemistry and pharmacology referred to but not explicitly described in this disclosure and examples are reported in the scientific literature and are well known to those skilled in the art. Matrix tablets are produced according to the process previously outlined in the detailed description of the preferred embodiments;
Example 1
Diltiazem hydrochloride ER tablets
% composition
Diltiazem hydrochloride
30
Natrosol 250 HHX
25
Carbopol 934P
10
Hydroxypropylmethyl cellulose K100M CR
33
Talc
1
Magnesium stearate
1
Diltiazem hydrochloride was blended with Natrosol and hydroxypropylmethyl cellulose in a high shear mixer until a homogeneous mixture was obtained. The mixture was granulated with isopropyl alcohol and dried in fluid bed dryer to a loss on drying of 1.5%. The dried granules were then passed through a sieve #14 mesh. The milled granules were blended with Carbopol, talc and magnesium stearate in a V-blender. Finally, the treated granules were pressed into tablets using a rotary tablet press.
Example 2
Tramadol ER tablets
% composition
Tramadol
40
Natrosol 250 HHX
15
Carbopol 934P
8
Hydroxypropylmethyl cellulose K100M CR
35
Talc
1
Magnesium stearate
1
Tramadol was blended with Natrosol and hydroxypropylmethyl cellulose in a high shear mixer until a homogeneous mixture was obtained. The mixture was granulated with isopropyl alcohol and dried in fluid bed dryer to a loss on drying of 1.5%. The dried granules were passed through a sieve #14 mesh. The milled granules were blended with Carbopol, talc and magnesium stearate in a V-blender. Finally, the treated granules were pressed into tablets using a rotary tablet press.
Example 3
Buspirone ER tablet
% composition
Buspirone hydrochloride
2.5
Natrosol 250 HHX
20
Lactose
17.5
Silicone dioxide
1
Carbopol 934P
10
Hydroxypropylmethyl cellulose K 100M CR
35
Ethylcellulose
5
Microcrystalline cellulose
7
Talc
1
The Buspirone was dissolved in isopropyl alcohol. Lactose was blended with Natrosol, ethylcellulose, microcrystalline cellulose, silicone dioxide and hydroxypropylmethyl cellulose in a high shear mixer until a homogeneous mixture was obtained. This mixture was granulated with the isopropyl alcohol Buspirone hydrochloride solution and dried in fluid bed dryer to a loss on drying of 1.5%. The dried granules were passed through a sieve #14 mesh. The milled granules were blended with Carbopol, talc and magnesium stearate in a V-blender. Finally, the treated granules were pressed into tablets using a rotary tablet press.
Although preferred embodiments of the invention have been described herein in detail, it is understood by those skilled in the art that variations may be made thereto without departing from the spirit of the invention of the scope of the appended claims. | The present invention relates to a controlled release pharmaceutical delivery device which provides sustained or pulsatile delivery of a selected pharmaceutically active substance for a predetermined period of time. The device comprises about 1 to 80% by weight covalently crosslinked water insoluble, water-swellable polymers and about 1 to 75% by weight uncrosslinked, linear water soluble polymers.
The invention also provides pharmaceutical compositions and methods for making such compositions in which a pharmaceutically active agent is incorporated into the delivery device. | 0 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a National Stage of International Application No. PCT/IB2010/051278 filed Mar. 24, 2010, claiming priority based on Italian Patent Application No. T02009A000231 filed Mar. 26, 2009, the contents of all of which are incorporated herein by reference in their entirety.
FIELD OF INVENTION
The present invention relates to a sensor apparatus intended to detect the level of a liquid, gel or powder substance contained in a receptacle.
More specifically the present invention relates to a sensor apparatus according to the preamble of claim 1 .
BRIEF SUMMARY OF THE INVENTION
Apparatus for detecting the level of a substance present in a receptacle, particularly in sectors such as the household appliances sector, are known in the present state of the art. For example, these apparatus are widely used in dishwashing machines for the purpose of detecting the level of rinsing agent, or salt, present inside the receptacles associated with a dispensing device or a limescale-removal device.
The apparatus of the type specified above make use of the combined action of an emitter and a receiver which are associated with a receptacle containing a liquid, gel or powder substance. The emitter is designed to emit radiation. The receiver, usually a photodiode or a phototransistor, is able to receive and convert into an electric signal radiation which is emitted by the emitter and the intensity of which is variable depending on the quantity or level of substance present in the receptacle.
Usually these apparatus have the function of indicating the reserve level of the liquid depending on the intensity of the radiation received. An optical device intended to reflect and/or refract the radiation depending on the refraction index of the means present in the receptacle and facing the optical device is typically arranged between the emitter and the receiver. In the case where the liquid means exceeds a predetermined threshold value, its level is situated facing the optical device and the radiation is mainly refracted through the liquid means, being dispersed. In the opposite case, its level is below the optical element and therefore the light radiation is mainly reflected towards the receiver which is able to indicate to a control circuit that a reserve level has been reached.
Although this type of apparatus envisages an electrical system for performing signalling to the machine, it does not provide at the same time a visual indication relating to the level of the substance present in the receptacle.
One object of the present invention is to provide a sensor apparatus of the abovementioned type which is able to provide also a visual indication of the level of the substance present in the receptacle in a way which can be directly seen by the user, is operationally reliable and can be manufactured in a simple and low-cost manner.
This object, together with others, is achieved according to the present invention by means of a sensor apparatus defined by the characteristic features contained in the accompanying claim 1 .
As a result of these characteristic features the sensor apparatus is able to exploit fully the same visible radiation emitted by the emitter both for an electric signal and for an optical signal which can be seen by a user.
BRIEF DESCRIPTION OF THE DRAWINGS
Further characteristic features and advantages of the present invention will become clear from the following detailed description provided purely by way of a non-limiting example, with reference to the accompanying drawings in which:
FIG. 1 is a perspective view of a dishwashing machine, the door of which includes a rinsing agent dispensing device provided with a receptacle which comprises a first example of embodiment of a sensor apparatus according to the present invention;
FIG. 2 is an enlarged and partly sectioned view along the line II-II of FIG. 1 of the dispensing device in the configuration corresponding to the condition where the door is open;
FIG. 2 a is a partial, schematic, cross-sectional view of the sensor apparatus along the line IIa-IIa of FIG. 2 ;
FIG. 3 is a view which is similar to that of FIG. 2 , but which shows the dispensing device in a second filling condition;
FIG. 3 a is a partial, schematic, cross-sectional view of the sensor apparatus along the line IIIa-IIIa of FIG. 3 ;
FIGS. 4 to 5 are partial schematic views which show two different variations of embodiment of the sensor apparatus according to the present invention;
FIG. 6 is a schematic cross-sectional view of a limescale-removal device with a receptacle which is provided with a second example of embodiment of a sensor apparatus according to the present invention and which is shown in a first filling condition; and
FIG. 7 is a view which is similar to that of FIG. 6 , but which shows the receptacle in a second filling condition.
DETAILED DESCRIPTION OF THE INVENTION
In FIG. 1 , 10 denotes overall a dishwashing machine of the type known per se.
The machine 10 generally comprises a housing 12 which has a substantially parallelepiped shape and which defines internally a washing chamber 14 which can be accessed via an open front side 16 of the housing 12 with which a closing door 18 is associated. The door 18 is hinged on the structure of the machine 10 along a horizontal axis X-X in the vicinity of its bottom horizontal side.
The door 18 is therefore capable of assuming a vertical position (not shown) in which it closes off the washing chamber 14 and a lowered position, shown in FIG. 1 , where it allows easy access to a device for dispensing washing agents, denoted overall by 20 .
In a manner known per se the dispensing device 20 is mounted on the inner side of the door 18 of the machine 10 . In this example of embodiment said dispensing device 20 is of the so-called integrated type, i.e. it comprises a single support structure or body 22 which contains both a device for dispensing a liquid or solid or powder washing agent and a device 26 for dispensing a rinsing or brightening agent.
The present invention is however not to be regarded as being limited to implementation in a device for dispensing washing agent integrated with an adjacent device for dispensing rinsing agent. In fact, as will become clear from the description below, the present invention may be applied to any receptacle intended to contain a liquid, gel or powder substance.
With reference to FIG. 2 , this shows partly cross-sectioned the dispensing device 26 for the rinsing agent.
The inner walls of the dispensing device 26 form a receptacle 28 defining an inner chamber 30 which contains a quantity of rinsing agent which—as shown in FIG. 2 —lies above a reserve threshold level. Furthermore, the receptacle 28 comprises a sensor apparatus 100 according to the present invention.
The sensor apparatus 100 is arranged in a wall of the receptacle 28 and comprises a support plate 102 which carries an emitter 104 and a receiver 106 .
As can be seen more clearly in FIG. 2 a , the sensor apparatus 100 also comprises an optical element, by way of example a triangular prism 108 preferably in the form of a right-angled triangle. Advantageously, the emitter 104 (for example an LED) and the receiver 106 are arranged facing the hypotenuse face or side 108 a of said triangular prism 108 . Instead the cathetus faces or sides of this triangular prism 108 define, respectively, a first reflective face 108 b and a second reflective face 108 c which are directed towards the inner chamber 30 of the receptacle 28 .
The sensor apparatus comprises furthermore an optical waveguide, for example a semi-transparent rod 110 , which is fixed to a portion of the receptacle 28 . The semi-transparent rod 110 emerges inside the chamber 32 in a position at least partly facing the triangular prism 108 . The semi-transparent rod 110 has advantageously a reflective face 112 which is inclined for example at about 45° with respect to its longitudinal axis and which faces the triangular prism 28 . This semi-transparent rod 110 terminates at the top on the lid with its signalling end 114 directed outwards.
Preferably the rectangular edge of the triangular prism 108 (i.e. the edge where the two reflective faces 108 b and 108 c intersect each other) is parallel to the longitudinal axis of the rod 110 .
The triangular prism 108 is able to couple optically the emitter 104 and the signalling end 114 which acts as an optical indicator which is visible in the manner which is described hereinbelow.
In the condition shown in FIGS. 2 and 2 a , the receptacle 28 has internally a level of rinsing agent above the signalling threshold of the apparatus 100 . The emitter 104 emits visible radiation L which is deviated so as to be reflected and refracted by the first reflective face 108 b of the triangular prism 108 in a first reflected fraction L 1 and a second refracted fraction L 2 , respectively. In this case, the level of the rinsing agent is above the surface of the triangular prism 108 . Therefore, the refraction index, which is present inside the chamber 30 and is influenced by the presence of the rinsing agent, is such that the fraction L 1 which is reflected and then deviated by the second reflective face 108 c has an intensity sufficient to activate the receiver 106 (advantageously a photodiode or a phototransistor). Furthermore the refracted fraction L 2 has a significant radiating intensity, but passing through the rinsing agent in liquid form is dispersed inside the chamber 30 , without managing to reach the semi-transparent rod 110 with an intensity sufficient to intercept the reflective face 112 so as to provide a visible indication at the signalling end 114 .
With reference to FIGS. 3 and 3 a (again relating to the horizontal position of the door 18 ), the receptacle 28 has internally a level of rinsing agent below the signalling threshold of the apparatus 100 . In this case, the level of the rinsing agent is below the surface of the triangular prism 108 . The refraction index of the prism 108 is therefore different from the previous index since there is no longer a liquid means which reaches the surface of the triangular prism 108 . Therefore the triangular prism 108 is formed so that—in this condition—the first reflected fraction L 1 has an intensity sufficient to activate the receiver 106 which sends to a control circuit (not shown) a signal indicating that the reserve level inside the receptacle 28 has been reached. At the same time, although the refracted fraction L 2 has a low intensity, it is however able to reach the reflective face 112 of the semi-transparent rod 110 which deviates the refracted fraction L 2 through it until it reaches the signalling end 114 . Therefore a visual signal which can be seen by a user looking at the receptacle 28 in the horizontal (or open) position of the door 18 is emitted.
Advantageously, the first reflective face 108 b and the second reflective face 108 c define planes which are perpendicular to each other.
With reference to FIG. 4 , this shows a first variation of embodiment of the sensor apparatus according to the present invention. Parts which are similar to those of the previous embodiment are indicated by the same reference numbers and/or letters.
In contrast to the preceding embodiment, the right-angled edge of the triangular prism 108 is parallel with a straight line perpendicular to the longitudinal axis of the optical waveguide 110 (lowered position of the door 18 ). Furthermore the emitter 104 and the receiver 106 are preferably fixed on the hypotenuse face 108 a of the triangular prism 108 .
With reference to FIG. 5 , this shows a second variation of embodiment of the sensor apparatus according to the present invention. Parts which are similar to those of the previous embodiment shown in FIGS. 1 to 3 are indicated by the same reference numbers and/or letters.
In contrast to the embodiment shown in FIGS. 1 to 3 , the optical element is a prism 108 which has a cross-section which is in the form of an isosceles trapezium. The emitter 104 and the receiver 106 are advantageously fixed to the large-base face 108 a of the prism 108 . Preferably the larger-base side of the prism 108 is parallel to the longitudinal axis of the optical waveguide 110 . The first reflective face 108 b and the second reflective face 108 c are defined by the oblique sides of the prism 108 .
Preferably, in the first and second variation of embodiment shown in FIGS. 4 and 5 , only the first reflective face 108 b is directed towards the inside of the container 28 .
Furthermore, the second reflective face 108 c has preferably a coating 120 suitable for optimising reflection towards the receiver 106 and minimising the refraction of the radiation striking the aforementioned second reflective face.
With reference to FIGS. 6 and 7 , these show a second embodiment of the sensor apparatus according to the present invention, denoted overall by 200 .
In this embodiment the sensor apparatus 100 is applied to a receptacle 300 of a limescale-removal device for dishwashing machines (details not shown). The sensor apparatus 200 comprises a first support plate 202 fixed onto a wall of the receptacle 300 and having an emitter 204 and a second support plate 203 fixed to the bottom of the receptacle 300 and having a receiver 206 directed towards the emitter 204 .
Furthermore, the apparatus has an optical waveguide, advantageously a semi-transparent rod 208 which is fixed in the region of the neck 302 of the container 300 by means of a plurality of radial spokes 304 . The semi-transparent rod 208 comprises a bottom reflective face 212 and a signalling end 214 which is directed towards the transparent lid 306 of the receptacle 300 . The semi-transparent rod 208 is arranged between the emitter 204 and the receiver 206 so that the radiation L′ emitted by the emitter 204 is directed towards the bottom reflective face 212 .
With reference to FIG. 6 , the level of the powder material present in the receptacle 300 exceeds the signalling threshold of the apparatus 200 and covers the semi-transparent rod 208 so that it obstructs the radiation L′ which is unable to reach the bottom reflective face 212 . In this way no radiation reaches either the signalling end 214 of the semi-transparent rod 208 nor the receiving device 206 .
With reference to FIG. 7 , the level of the powder material present in the receptacle 300 exceeds the signalling threshold of the apparatus 200 . In this condition, the level of powder material is below the bottom reflective face 212 . Consequently, the radiation L′, which is within the visible spectrum, is transmitted by the reflective face 212 in a first fraction L′, which continues its path towards the receiver 206 , and a second fraction L 2 ′. The reflected fraction L 2 ′ passes along the length of the semi-transparent rod 208 and lights up the signalling end 214 . The reflected fraction L 2 ′ is directed towards 206 and has an intensity such as to activate it so as to signal a reserve level of powder material to a control circuit (not shown). In this way the semi-transparent rod 208 acts not only as an optical waveguide for the signalling end 214 , but also as an optical element for selectively coupling this signalling end 214 to the emitter 204 .
Obviously, without affecting the principle of the invention, the embodiments and the constructional details may be greatly modified with respect to that described and illustrated purely by way of a non-limiting example, without thereby departing from the scope of the invention as defined in the accompanying claims. | The sensor apparatus is intended to detect the level of a liquid, gel or powder substance contained in a receptacle and includes an emitter able to emit radiation and a receiver able to receive and convert into an electric signal radiation which is emitted by the emitter and the intensity of which is variable depending on the quantity or level of substance present in the receptacle. The emitter is designed to emit visible radiation and the apparatus also includes a visible optical indicator and an optical element able to couple optically the emitter to the optical indicator so that, when the quantity or level of the substance in the receptacle is lower than a predetermined threshold, a fraction of the radiation generated by the emitter is able to light up the optical indicator. | 6 |
BACKGROUND
1. Technical Field
The present invention relates to double fabric blinds and, more particularly, to a device for adjusting a fabric angle of double fabric blinds.
2. Background Art
Referring to FIGS. 1 and 2 , double fabric blinds generally use a double fabric, in which a front sheet 1 and a rear sheet 2 woven from mesh are coupled to a plurality of connection fabrics 3 extending between the front sheet 1 and the rear sheet 2 , as a fabric for blinds 4 wound around a winding rod 6 . Each of the connection fabrics 3 has a substantially S-shaped section and is connected in the longitudinal direction such that the front sheet 1 is spaced at a predetermined distance apart from the rear sheet 2 . The front and rear sheets 1 and 2 are formed from a transparent material woven from mesh, and the plurality of connection fabrics 3 are formed from a translucent material which is more flexible than those of the front and rear sheets 1 and 2 . The fabric 4 for the double fabric blinds allows light from the outside to be transmitted therein via the front and rear sheets 1 and 2 when the connection fabrics 3 are spread.
As illustrated in FIG. 2 , when one of the front and rear sheets 1 and 2 moves upward, the various connection fabrics 3 are folded, and thus the front sheet 1 and the rear sheet 2 are almost in contact with each other. Simultaneously, since the plurality of connection fabrics 3 are in contact with each other, the blinds enter a translucent state in which light is transmitted through the front and rear sheets 1 and 2 , but is at least partially obscured.
Turning to FIG. 3 , roll blinds 9 have been manufactured by using the fabric 4 of the double fabric blinds. Roll blinds 9 can include an upper case 6 , which is coupled to the winding rod 5 for winding the fabric 4 of the double fabric blinds, and a lower end bar 7 having a weight on the lower end of the double fabric. Also, a driving roller 8 is disposed on one end of the winding rod 5 so as to move the double fabric in the vertical direction, and an adjustable string 8 a for rotating the driving roller 8 is provided. In this state, when the adjustable string 8 a is pulled, the double fabric for blinds 4 moves downward while the driving roller 8 is rotated. The connection fabric 3 disposed between the front sheet 1 and the rear sheet 2 moves downward in the folded state, and when the fabric for blinds 4 moves down to the bottom, the folded connection fabrics 3 are spread due to the weight of the lower end bar 7 .
Since conventional roll blinds have a structure in which a plurality of vanes are spread due to the weight of the lower end bar only when the double fabric moves down to the bottom, there is a limitation in that the roll blinds include no elements for allowing a user to spread the folded connection fabric at a desired position, particularly at the middle or upper positions of the double fabric, and/or adjust a spread angle of the connection fabric. Also, the conventional design includes a drop-down string (adjustable string 8 a ) which poses a safety hazard for children who may become entangled in the string.
To solve the abovementioned limitation, “blinds with adjustment for the angle of a double fabric” are disclosed in Korean patent gazette No. 10-943408, a previously owned patent also owned by the present applicant. Since the double blinds of the previously registered patent include a driving body, an angle adjustment component, two rollers, and two adjustable strings, the structure of the blinds in this configuration is relatively complicated. Although a degree of openness of the front sheet of the double fabric is adjustable via a friction member of the angle adjustment component, the abrasiveness (and associated coefficient of friction) of the friction member may deteriorate after being used for a long time, reducing the degree of openness to which the double fabric can be adjusted.
BRIEF SUMMARY
One Aspect of the present invention provides adjusting of double fabric blinds and, more particularly, a device for adjusting the fabric angle of the double fabric blinds, which is capable of finely adjusting a degree of openness of such a fabric since a plurality (e.g., four or eight) of balls are sequentially held and inserted in a holding groove of a rotation component, and are rotated in a guide groove of a stopper at 90 degrees or 45 degrees, thereby reducing accidents since an adjustable string is not used. Also, the device can be easily operated since a separate lower end bar is formed on the lower ends of the front sheet and rear sheet, which can provide the same function as a handle.
To achieve the abovementioned functions, embodiments of the present invention provide a device for adjusting the fabric angle of double fabric blinds, comprising: a cover provided with an insertion hole having a hook protrusion formed therein, wherein coupling protrusions are disposed symmetrical to each other on the inner circumferential surface of the cover and protrude outward; a rotation component having coupling grooves which are coupled to the coupling protrusions of the cover, disposed symmetrical to each other on the outer circumferential surface of the rotation component, and recessed inward, and insertion grooves and a coupling hole formed in the inner circumferential surface of said rotation component, wherein a plurality of balls are inserted into the insertion grooves and a stopper is coupled to the coupling hole; a stopper having a shaft insertion hole which passes through same and has a coupling groove coupled to the hook protrusion of a spring at the lower end of said stopper, so as to be inserted into the coupling hole of the rotation component, and guide grooves, inclined grooves, and holding grooves in the outer circumferential surface of same, wherein the guide grooves and inclined grooves allow the balls to be rotated, and the holding grooves hold the balls; a fixing shaft, the front of which has the coupling protrusion coupled to a washer and the rear of which has the spring coupled to the hook protrusion projecting outward, inserted into the shaft insertion hole of the stopper; and blinds which have the plurality of balls inserted into the insertion grooves of the rotation component, to adjust the angle of the double fabric by moving in the guide groove and coupling the stopper to the rotation component. The device is characterized in that when the rotation component is rotated after four balls are inserted into the guide groove of the stopper and the rotation component is coupled to the stopper, a degree of openness of the double fabric is adjusted while the four balls are sequentially held by the holding groove as the rotation component is rotated at 90 degrees.
The present invention can provide the following technical effects.
First, a user may easily and simply adjust the degree of openness of the double fabric as desired.
Second, the opened angle of the double fabric may be finely adjusted by controlling the number of the balls inserted into the insertion grooves of the rotation component.
Third, the device of the present invention is effective in that a ball chain or an adjustable string is not used, thereby improving safety for the user.
Fourth, the device has a simple structure and reduces malfunctions from occurring during operation, thereby also reducing manufacturing costs.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1-3 are views illustrating a configuration and operation of conventional double fabric blinds.
FIG. 4 is a cross-sectional view illustrating double blinds of applicant's previously registered patent disclosed in Korean patent gazette No. 10-943408.
FIG. 5 is a perspective exploded view illustrating the configuration of a device for adjusting a fabric angle of double fabric blinds according to embodiments of the present invention.
FIG. 6 is a cross-sectional view illustrating a configuration of the device for adjusting the fabric angle of double fabric blinds according to embodiments of the present invention.
FIG. 7 is a perspective view illustrating a state in which a rotation component is coupled to a cover of the device for adjusting the fabric angle of double fabric blinds according to embodiments of the present invention.
FIG. 8 is a perspective view illustrating a state in which all elements of the device for adjusting the fabric angle of double fabric blinds according to embodiments of the present invention are coupled to each other.
FIGS. 9-15 are views illustrating a state in which the device for adjusting the fabric angle of double fabric blinds according to embodiments of the present invention is used.
DETAILED DESCRIPTION
Hereinafter, the preferred embodiments of the present invention will be described below in more detail with reference to the accompanying drawings.
Reference number 300 represents a body of a device for adjusting a fabric angle of double fabric blinds according to embodiments of the present invention. The body 300 includes: a cover 310 having a hook protrusion 312 on which a coupling protrusion 311 is formed; a rotation component 320 having an outer circumferential surface on which coupling grooves 321 disposed symmetrically relative to each other are formed, and an inner circumferential surface in which an insertion groove 322 and a coupling hole 323 are formed; a stopper 330 having a shaft insertion hole 332 and a coupling groove 331 formed on one surface of the outer circumferential surface of the stopper 330 ; the stopper having a guide groove 333 , an inclined groove 334 , and a holding groove 335 formed on the outer circumferential surface thereof, wherein a ball 350 is rotated in the guide grooves and inclined grooves 333 and 334 and held in the holding groove 335 ; and a fixing shaft 340 , the front of which has a coupling protrusion 342 coupled to which a washer 341 and the rear of which is coupled to a spring 344 having a hook protrusion 343 protruding outward.
The cover 310 has an insertion hole and a hook protrusion in which coupling protrusions are formed symmetrical to each other on the inner circumferential surface of the cover, protruding outward. Also, a plurality of protrusions 314 coupled to a winding drum around which the double fabric is wound are formed on the outer circumferential surface of the cover 310 . Any desired number of protrusions 314 can be provided on cover 310 . The coupling grooves 321 , which are symmetrical to each other and can be in the form of semicircular grooves, are formed in the outer circumferential surface of the rotation component 320 . The coupling hole 323 having the insertion grooves 322 , where a plurality of balls 350 are inserted, can be formed in the inner circumferential surface of the rotation component.
The insertion groove 323 can have a semicircular shape and extend in a longitudinal direction within the rotation component 320 , which is illustrated in FIG. 6 . Also, the plurality of balls 350 can be inserted into the insertion groove 323 and used as discussed herein. In particular, four balls 350 can be inserted into the insertion groove, or eight balls 350 may alternatively be inserted for use. In other embodiments, more than eight balls 350 may be used if desired. The fixing shaft 340 is inserted into the coupling hole 323 of the rotation component 320 . The stopper 330 is a pipe which can have a cylindrical shape. The coupling groove 331 , to which the hook protrusion 343 of the spring 344 is coupled, is formed on one area of the inner circumferential surface of the stopper and has a predetermined length. The shaft insertion hole 332 is formed in the stopper. The guide grooves and inclined grooves 333 and 334 , in which each of the balls 350 is moved, and the holding groove 335 for holding the ball 350 are formed in the outer circumferential surface of the stopper 330 .
One surface of the ball 350 contacts the guide groove 333 of the stopper 330 , and another surface of the ball contacts the insertion groove 322 of the rotation component 320 . Thus, the rotation component 320 may hold a rotation according to the movement of the ball 350 . The coupling protrusion 342 , to which the washer 341 is coupled, is formed on the front of the fixing shaft 340 , and the spring 344 having the hook protrusion 343 protruding outward is coupled to the rear of the fixing shaft. A coupling groove 345 is formed in the central portion of the rear surface of the shaft 340 so that a coupling protrusion of a bracket is inserted. The hook protrusion 343 of the spring 344 can be disposed on the outer circumferential surface of the fixing shaft 340 and coupled to the coupling groove 331 of the stopper 330 as described above, and thus, the stopper 330 is held by the hook protrusion.
A method for operating the abovementioned device to adjust the fabric angle of the double fabric blinds according to embodiments of the present invention will be described with reference to FIGS. 9-13 . First, the coupling protrusion of the bracket is coupled to the coupling groove 345 formed in the rear surface of the fixing shaft 340 , and a rotor rotated due to the elastic force of a well-known spring is mounted on a spring on a surface opposite the rear surface of the fixing shaft. Further, the winding drum, around which a double fabric 110 made of a connection fabric 113 connecting a front sheet 111 and a rear sheet 112 is wound, may be coupled and fixed to the protrusion 314 of the cover 310 . Lower end rods 371 and 372 are provided on the lower ends of the front and rear sheets 111 and 112 , respectively. Each of the lower end rods 371 and 372 can have a cylindrical shape and the same length as the width of the fabric. A string provided with a handle may be provided at the lower side of the lower end rod 371 of the front sheet for use.
As illustrated in FIGS. 9 and 10 , the lower end rod 371 of the front sheet may be gripped and pulled downward in a state in which the double fabric 110 is entirely wound around the winding drum, thereby moving the double fabric in the vertical direction. The four balls 350 located in a front side of the insertion groove 322 of the rotation component 320 are rotated in the guide groove 333 of the stopper 330 . Simultaneously, the double fabric moves downward while the rotor on the opposite side is loading the spring. The fixing shaft 340 is in a fixed state, and the stopper 330 is rotated in a direction opposite to that of the spring 344 wound in a state in which the hook protrusion 343 of the spring 344 is coupled to the stopper. Simultaneously, the double fabric moves downward while the rotation component 320 is engaged with the stopper 340 and the four balls 350 , and the cover 310 inserted into the coupling groove 321 of the rotation component 320 are rotated in the same direction.
To allow sunlight to be transmitted to the inside by adjusting an degree of openness of the double fabric 110 in a state in which the double fabric 110 has moved downward to the lowest end, when the lower end rod 372 of the rear sheet is gripped and pulled downward as illustrated in FIG. 11 , a first ball 350 of the four balls 350 moves along the inclined groove 334 and is located and stopped in the holding groove 335 as illustrated in FIG. 12 , and simultaneously, the front sheet 111 moves upward to open the double fabric 110 as illustrated in FIG. 13 . In particular, the first ball 350 of the four balls is held in the holding groove 335 when the rotation component 320 is rotated by 90 degrees to adjust the degree of openness of the double fabric, and when the lower end rod 372 of the rear sheet is pulled downward again, a second ball 350 is held in the holding groove 335 when the rotation component 320 is rotated by 90 degrees to further increase the degree of openness of the double fabric.
As described above, as the rotation component 320 is rotated by 90 degrees, the plurality of balls 350 may be sequentially held in the holding groove 355 to finely adjust the degree of openness of the double fabric. Also, according to embodiments of the present invention, eight balls 350 can be coupled to the insertion grooves 322 of the rotation component 320 , and the stopper 330 is inserted into the rotation component 320 , and thus the balls 350 are located in the guide groove 333 formed in the outer circumferential surface of the stopper 330 . In this state, as illustrated in FIG. 11 , when the lower end rod 372 of the rear sheet is gripped and pulled downward, the first ball 350 of the eight balls is held in the holding groove 335 when the rotation component 320 is rotated by 45 degrees to adjust the degree of openness of the double fabric, and when the lower end rod 372 of the rear sheet is pulled downward again, the second ball 350 is held in the holding groove 335 when the rotation component 320 is rotated by 45 degrees to further open the degree of openness of the double fabric.
As described above, as the rotation component 320 is rotated by 45 degrees, the eight balls 350 may be sequentially held in the holding groove 355 to finely adjust the degree of openness of the double fabric. In this state, when the lower end rod 372 of the rear sheet is pulled downward such that the roller turns more than a holding angle, the ball 350 is removed from the holding groove 335 as illustrated in FIGS. 14 and 15 . Simultaneously, the rotor on the opposite side is rotated as the spring loses its tension. The cover, to which the winding drum is coupled, is rotated and causes the double fabric 110 to move upward. The ball 350 may be located in the guide groove 333 of the stopper 330 , which is the initial state. | The present invention relates to double fabric blinds and, more particularly, to a device for adjusting a fabric angle of the double fabric blinds, which is capable of finely adjusting an degree of openness of a front sheet, wherein a plurality of balls are sequentially held in a holding groove, e.g., as four or eight balls, inserted into an insertion groove of a rotation component, wherein the plurality of balls are rotated in a guide groove of a stopper by approximately 90 degrees or 45 degrees, thereby improving safety and omitting the use of a conventional string. | 4 |
GOVERNMENT RIGHTS
This application was made with U.S. Government support under Contract No. HSHQDC-05-C-00004 by the U.S. Department. of Homeland Security. The Government may have certain rights under the subject invention.
FIELD OF THE INVENTION
This invention relates to a system and method for detecting hazardous atmospheric constituents.
BACKGROUND OF THE INVENTION
Real-time air sampling and analysis especially to detect toxic or lethal constituents is a challenging problem. The sampling must be fast to prevent injury or even loss of life yet must be sure in order to prevent false positives which could trigger false alarms resulting in huge unnecessary displacement of people and equipment. Measuring ultraviolet (UV) fluorescence is one technique that is sensitive but is not highly accurate. Infrared (IR) absorbance is another method which is more accurate but not so fast. IR spectroscopy has greater capability to discriminate against normally occurring background clutter that sets off UV fluorescence detectors. In addition to speed and accuracy of detection continuous monitoring is also often desirable or required.
SUMMARY OF THE INVENTION
In accordance with various aspects of the subject invention in at least one embodiment the invention presents an improved aerosol sampling system and method for detecting constituents in air which is fast, accurate and reduces false positives.
The subject invention results from the realization, in part, that an improved faster, surer sampling can be achieved by counting particles in the air to be sampled and then measuring the UV fluorescence of the sample only if the particle count is above a predetermined threshold, measuring the IR absorbance of that sample and then triggering a threat alarm only if the IR spectral absorbance is matched to that of a target within a predetermined threshold, or if the UV and IR responses are both above their respective thresholds; alternatively, the IR response can be measured only if the UV fluorescence measured is above the UV fluorescence threshold and the threat alarm triggered only if the measured IR response is above the required threshold.
The subject invention, however, in other embodiments, need not achieve all these objectives and the claims hereof should not be limited to structures or methods capable of achieving these objectives.
This invention features an air sampling system for atmospheric constituents including a particle counter for counting particles present in the atmosphere, a UV detection unit, an IR detection unit, a collection apparatus for accumulating samples of particles from the air and presenting them to the UV and IR detector units, a pump system for moving air to be sampled to the particle counter and to the collection apparatus, and a controller for actuating the collection apparatus to present the sample to the UV detector unit and the IR detection unit only if the particles counted in the particle counter exceed a predetermined value, and indicating a threat alarm only if the IR detector unit and UV detector unit measure responses of the collected samples that exceed predetermined UV and IR thresholds, respectively.
In a preferred embodiment the particle counter may include a filter to exclude particles greater than a pre-selected size. The pre-selected size may be 10 microns. The collection apparatus may include a substrate for accumulating particles from air to be sampled for a predetermined duration and a mechanism for moving the substrate selectively to each of the detector units. The UV detector unit may measure UV fluorescence back-scatter in a predetermined wavelength range. The predetermined UV wavelength detector range may be 300-500 nm. The predetermined wavelength excitation range may be approximately 280-365 nm. The IR detector unit may measure IR absorption in either transmission or reflection over a predetermined wavelength range. The predetermined IR wavelength range may be 2.5-12 microns. The IR detector unit may include an IR absorption spectrometer. The collection apparatus may include an impactor for accumulating samples. The controller may actuate the collection apparatus to present a sample, first, to the UV detector unit and then to the IR detector unit only if the UV detector unit measures UV fluorescence of the sample exceeding a predetermined threshold.
The invention also features a method of sampling constituents in air including counting particles in the air to be sampled, collecting samples of accumulated particles, measuring UV response of a sample of accumulated particles only if the particle count exceeds a predetermined threshold, measuring IR spectral response of that sample, and indicating a threat alarm if the IR response matches that of a target within a predetermined threshold.
In a preferred embodiment particles larger than a predetermined size may be excluded from the counting. The predetermined size may be 10 microns. The UV fluorescence may be measured in a predetermined UV wavelength range. The predetermined wavelength range may be 300-500 nm. The IR absorbance may be measured in a predetermined IR wavelength range. The pre-selected IR wavelength range may be 2.5-12 um. The IR response may be measured by absorption spectroscopy in either reflection or transmission. The IR absorbance of the sample may be only measured if the measured UV fluorescence exceeds a predetermined threshold.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
Other objects, features and advantages will occur to those skilled in the art from the following description of a preferred embodiment and the accompanying drawings, in which:
FIG. 1 is a process flow diagram of an air sampling method and system according to this invention;
FIG. 2 is a view similar to FIG. 1 using alternative process logic;
FIG. 3 is a logic flow diagram of an air sampling method according to this invention;
FIG. 4 is a schematic block diagram of an air sampling system according to this invention; and
FIG. 5 is a three dimensional view of an apparatus for implementing the air sampling system according to this invention.
DETAILED DESCRIPTION OF THE INVENTION
Aside from the preferred embodiment or embodiments disclosed below, this invention is capable of other embodiments and of being practiced or being carried out in various ways. Thus, it is to be understood that the invention is not limited in its application to the details of construction and the arrangements of components set forth in the following description or illustrated in the drawings. If only one embodiment is described herein, the claims hereof are not to be limited to that embodiment. Moreover, the claims hereof are not to be read restrictively unless there is clear and convincing evidence manifesting a certain exclusion, restriction, or disclaimer.
There is shown in FIG. 1 one process flow diagram 10 according to this invention, which begins with the air flow in 12 to a particle counter 14 which may include a filter 16 that filters out large particles above some size, for example 10 microns. The air is then submitted to the particle counter 18 . If the particle count is below a certain level, no further action is taken; if it is above a certain level then a collection apparatus 20 is actuated. The collection apparatus may include a linear virtual impactor which receives the air on a substrate and collects particles; it also pre-concentrates particles in the correct size range. This results in a major and minor air flow. The major portion of the air flow, after passing through the linear virtual impactor or other collection apparatus, exits as indicated at the air flow out 22 . There may be a particle counter ambient threshold detector 24 . This is used to keep track of the ambient particle count as it varies during the day and from day to day and week to week so that the particle count at 18 can be more accurate. For example, if there were construction going on during the day in an airport where this device was installed the particulate matter in the air during the day might be very high and so the high particle count would exceed its threshold every time, which would not be an accurate representation. In that case the particle counter ambient threshold detector 24 would note a raised ambient level which can then be used to adjust the threshold high particle count. Practically, the threshold is set at some percentage of the ambient particle level. A typical count in a typical ambient condition, would be, for example, 100 particles per liter of air in the 1-10 micron size range (respirable size range). Once the collection apparatus 20 has been actuated a portion of the flow, the minor flow, is directed as indicated at 26 so that the substrate containing the sample of particles 28 is submitted now to a UV detector 30 . UV detector 30 may seek to detect the fluorescence back-scatter of the particles in a particular wavelength range, for example, 300-500 nm, but it not limited to this range, with a UV excitation wavelength of, for example, 365 nm, but is not fixed at this value. If the UV fluorescence threshold for the sensitivity of the sample is not met 32 no further action may be taken as indicated at 34 and the substrates will be referred back for cleaning. The UV threshold sensitivity may be, for example some number of photons above the background response of the substrate. If the threshold is met then in this embodiment the IR spectral absorption of the particles on the sample is measured either in reflection or transmission 36 . The particular IR wavelength range shown in FIG. 1 is 5.5-11 um, but the detector may operate anywhere between 2.5 and 100 um, but is not limited to this range and can be any appropriate range in the infrared spectrum. The IR threshold response for the sample particles, may be for example, based on a degree of “matching” or correlations between the sample absorption spectrum and target threat absorption spectrum, both of which are normalized/corrected so as to take amplitude or offset out of the equation. Typically, a reliable decision or correlation requires a sample of approximately 1,000 particles. If the IR threshold is not met 38 , then the system may at this time take no further action as at 40 and the substrates will be referred back for cleaning. If it is met then a threat may be detected 42 and if it is a threat, an alarm is triggered 44 . If no threat was detected the substrates are cleaned of all sample particles 46 and the collection apparatus returns to its quiescent state. In FIG. 1 the particle count is the first screening. If the particle count threshold is not reached then no UV detection is effected. The UV detection actually functions as a second screen for if the UV detection does not find the particle sample sensitivity to be above a certain threshold the IR spectroscopy will not occur.
In another embodiment, however, as shown in FIG. 2 , process flow diagram 10 a is essentially the same except for the portion following the collection of the particles 28 . In flow process diagram 10 a after the collection of the particles on the substrate 28 both the UV detection 30 and IR detection 36 are instituted simultaneously, then the output on each is checked to see whether the UV threshold 50 has been met in one case and the IR threshold 52 has been met in the other. If both thresholds have been met then AND gate 54 will pass the information to the threat detection operation 42 which will trigger a threat alarm 44 . If both thresholds are not met, AND gate 54 does not provide the affirmative signal, so a threat is not detected 42 , no further action is taken and the substrates will be referred for cleaning 46 . A pumping system provides both the major air flow through the particle counter and the linear virtual impactor collector and the minor flow through the collection apparatus. The pumping system may include a pump for each.
A flow chart 100 depicting the method of the invention is shown in the FIG. 3 . This description begins with the particle count 102 . If the particle count does not meet or exceed the threshold 104 the system returns to the particle count operation 102 . If it does exceed the threshold a pump is actuated 106 to begin the flow to the linear virtual impactor to accumulate the sample particles on the substrate. The particle counter that does the particle counting 102 typically has its own internal pump, which is operating continuously. Once the pump is activated the collection apparatus is also actuated 108 and the particles are collected on a substrate 110 . The collection apparatus then moves the substrate to a first station for UV analysis 112 . If no threat is detected there 114 the substrate is cleaned 116 and referred back to the particle count operation 102 . If a threat is detected then an inquiry is made as to whether the particle count is sufficient for an IR analysis 118 ; if not additional particles are collected 120 and then an IR analysis is done 122 . If the IR analysis indicates a sensitivity of the sample particles above a certain threshold 124 then a threat alarm is triggered 126 ; if not the system refers on line 128 to clean the substrate 116 and return to the particle count operation 102 .
A schematic block diagram of the system according to this invention is shown in FIG. 4 including a particle counter 150 which has its own pump 152 , a system pump 154 and a UV detector unit 156 including a UV source 158 and UV detector 160 . Typically, this is a reflective detector. Also shown is the IR detector unit 162 including an IR source 164 , an IR detector 166 and IR analyzer 168 . The analyzer may be a spectrometer which measures sample absorbance at the desired frequencies to identify whatever contaminates or constituents the system is set to detect in aerosols. The collection apparatus 170 includes a linear actuator or other device which can move a substrate from a collection point, where, for example, the linear virtual impactor can load the sample particles onto a substrate and then the linear actuator moves the substrate to the UV detector unit 156 and the IR detector unit 162 . The entire system 148 is operated by controller 171 which may be a PC, for example. Controller 171 monitors particle counter 150 . If the particle count goes above a particular threshold it turns on the pump and operates collection apparatus 170 to bring a substrate in front of the impaction nozzle being supplied by pump 154 , where upon a number of sample particles are collected on to the substrate from the air for a predetermined duration dependent on the inlet concentration. Controller 171 now moves collection apparatus to bring the substrate to the UV detector unit 156 and the IR detector unit 162 . It monitors the output of both the UV 156 and IR 162 detector units. IF both units find a response in the sample particles above some threshold level the controller determines that a threat alarm is necessary as indicated previously with respect to FIG. 1 , for example. The UV detection unit having met its threshold may be a precondition to the operation of IR detection unit 162 or they may both be operated simultaneously and a threshold-met indication from both may be required to produce a threat alarm.
In one particular embodiment the system 148 a , FIG. 5 is implemented using aerosol particle counter 150 mounted on a housing base 180 along with the other components. Particle counter 150 has an inlet 202 for inducting air and a collection apparatus 170 including linear actuator 182 which moves the substrate 184 in a removable holder from the particle deposition nozzle 186 to the UV detector unit 156 and the IR detector unit 162 . An auxiliary pump 188 is provided for the minor flow while the pump 152 , FIG. 4 , provides the flow for the particle counter. The optical particle counter 150 flow and major flow have to be independent: the counter 150 flow is always on, while the major flow for the linear virtual impact collector is supplied by pump 154 . The UV detector unit 156 includes both the source 158 and detector 160 . The IR detector unit 162 includes an infrared spectrometer 190 and an infrared transmission microscope 192 . The infrared source appears at 194 .
Although specific features of the invention are shown in some drawings and not in others, this is for convenience only as each feature may be combined with any or all of the other features in accordance with the invention. The words “including”, “comprising”, “having”, and “with” as used herein are to be interpreted broadly and comprehensively and are not limited to any physical interconnection. Moreover, any embodiments disclosed in the subject application are not to be taken as the only possible embodiments.
In addition, any amendment presented during the prosecution of the patent application for this patent is not a disclaimer of any claim element presented in the application as filed: those skilled in the art cannot reasonably be expected to draft a claim that would literally encompass all possible equivalents, many equivalents will be unforeseeable at the time of the amendment and are beyond a fair interpretation of what is to be surrendered (if anything), the rationale underlying the amendment may bear no more than a tangential relation to many equivalents, and/or there are many other reasons the applicant can not be expected to describe certain insubstantial substitutes for any claim element amended.
Other embodiments will occur to those skilled in the art and are within the following claims. | A system and method for sampling constituents in air including counting particles in the air to be sampled; collecting samples of accumulated particles; measuring UV response of a sample of accumulated particles only if the particle count exceeds a predetermined threshold; measuring IR response of that sample; and indicating a threat alarm if the IR response matches that of a target within a predetermined threshold. | 6 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Patent Application No. 60/802,171, filed May 22, 2006, the contents of which are hereby incorporated herein by reference in their entirety.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] This invention relates to building closures, such as doors and windows, in general, and relates to fireproof closures in particular.
[0004] 2. Related Art
[0005] A fireproof door or window is a self-closing barrier designed to prevent the penetration of fire and smoke in through openings in walls for a given period of time. As used herein, the term “fireproof” refers to this ability to prevent the penetration of fire and smoke in through openings in walls for a given period of time, and not to any absolute ability to stop fires from spreading for an extended time.
[0006] There are many types of fireproof doors which are currently available. These doors are entitled to a fireproof rating based on criteria established by various standards setting organizations, such as the Underwriter's Laboratories, Inc. (UL). Typically, the doors must pass a burn test that is applied to one side of a door at a specified high temperature for a certain period of time while keeping heat from the other side of the door. However, in addition to keeping out the heat, in practical applications the doors must also keep smoke from passing through the door opening. As is well known, it is usually smoke inhalation that people die from in fires. Both requirements are difficult to achieve while at the same time retaining the primary function of a door, which is to be operable to permit egress between the spaces the door divides. If the door is too tight against its frame, then it is difficult to operate. If the door is made of a nonflammable material, such as metal or concrete, then it becomes heavy and is usually not conducive to a decorative environment. Thus, as with most doors, there is always a compromise in door thickness, materials and overall weight in order to achieve a certain level of fireproofing (for example, a fire-resistance time, such as 90 minutes).
[0007] Prior art fireproof doors usually include an exterior frame and covering with an internal core. Such doors can use an internal insulation layer consisting of compressed fireproof materials which practically fill out the space within the frame of the door. These known fireproof doors are relatively expensive and can be so heavy in weight that they can be opened and closed only with extreme effort. Another type of door uses an insulation layer made of an elastic, flexible, fireproof textile fabric fixed inside of a metal frame. See for example U.S. Pat. No. 4,270,326, which is incorporated herein by reference in its entirety.
[0008] Some modern fire proof doors use an intumescent material, such as one made from hydrated sodium silicate, which expands with the development of foaming pressure as a reaction to heat. Other intumescent materials include foaming/expanding graphite; and poly-ammonium phosphates. When heated, such as by a fire, a fine-porous, compression-resistant, non-combustible, and heat-sealing foam is formed. This foam fills joints and gaps in the immediate vicinity, and thus prevents the penetration of fire and smoke for a certain period of time. The material can be obtained commercially in sheets, or can be “blown in” as a powder. For example, this material has been used as an edge band in regular doors and French doors, so as to seal the space between a closed door and its frame where there is a fire. Thus, where intumescent strips or sections of the material have been attached onto or inserted into the edges of wooden or steel doors, gateways, and flaps, in the event of a fire, they rapidly expand and reliably seal off joints and gaps in a short time.
[0009] Most fire proof doors are solid, because the prior art teaches that the thicker the door, the greater will be the effectiveness of the door as a fire door, and consequently the greater will be the fire rating. Unfortunately, thicker doors and solid doors are often heavy, and can be expensive. Also, the artistic level of such doors is also quite limited. For example, there is a teaching away from the use of doors that have louvers and other ventilation structures, since ventilation openings are thought to make a door unusable as a fireproof door. Conventional wisdom suggests that a louvered or otherwise ventilated or vent-providing, door cannot function as an effective fire door. There is no known louvered door that can be thought of, much less labeled as, a wooden fireproof louver door. Moreover no louver itself are known to have been fire-rated and installed in a fireproof door.
SUMMARY OF THE INVENTION
[0010] The presently disclosed apparatus, systems, and methods solve the problem of providing a door with both a ventilation function and a fireproof function. The present disclosure teaches a door that can be economically manufactured. Such a door is attractive and readily available for decorative applications, provides the expected air flow during normal times, is rugged and solid, yet is relatively light weight for a fire proof door. The present disclosure, for the first time, teaches a fireproof louvered door.
[0011] The present disclosure teaches a fireproof louver panel that comprises a panel frame and a plurality of longitudinally extending slats attached to the panel frame. One or more of the slats comprises a shell and an intumescent layer that expands under heat to form an airtight seal. In some aspects, the longitudinally extending slats have a thickness, angle, and spacing sufficient to form said airtight seal when subjected to heat. As non-limiting examples, the thickness may be from 0.05 to 0.5 inches, or may be about 0.25 inches, the angle may be from about 30 degrees to 75 degrees, or may be about 60 degrees, and the spacing may be from 0.05 to 0.5 inches, or may be about 0.25 inches.
[0012] In some aspects, the longitudinally extending slats are perpendicular to the plane of the door and have a thickness and spacing sufficient to form an airtight seal when subjected to heat. In some aspects, the shell comprises at least one opening through which the intumescent layer expands under heat. The opening may be shaped to cause the intumescent layer, when under heat, to expand in the plane of the door. In some aspects, the shell breaks open when the intumescent layer expands under heat. In some aspects, the intumescent layer is inside an inner cavity of the shell.
[0013] In some aspects, the shell has an upper layer and a lower layer, and the slat comprises an outer skin which surrounds the upper layer, the lower layer, and the intumescent material. In some aspects, the outer skin comprises a wrapping material structurally configured to open at a chosen location during expansion of the intumescent layer.
[0014] The intumescent material may, as non-limiting examples, be selected from hydrated sodium silicate; foaming graphite; expanding graphite; poly-ammonium phosphates; and combinations thereof.
[0015] In some aspects, the intumescent material forms a non-combustible heat-sealing foam when heated. In some aspects, the slats are jalousie-type slats.
[0016] The present disclosure also teaches a fireproof door having an external frame, an internal core of a fireproof material (among other materials), and a fireproof louver panel. In some aspects, a further intumescent layer is disposed at the outside of the external frame, and the intumescent material and the further intumescent material provide an airtight seal extending beyond the dimensions of the external frame. In some aspects, the door has a window disposed in a window opening, and a fireproof louver panel is disposed in the window opening adjacent the window.
[0017] The present disclosure further teaches a fireproof window having an external frame, a flat translucent internal core of a fireproof material (among other materials), and a fireproof louver panel adjacent a flat side of the flat translucent internal core.
[0018] The present disclosure teaches a method of fireproofing an opening. A movable fireproof closure is affixed in the opening. The closure has a first intumescent layer attached at the exterior of the closure and a panel frame within the closure. The panel frame has attached to it one or more longitudinally extending slats having second intumescent layer. Placement of the first and second intumescent layers is then configured so that the opening is sealed when the first intumescent layer and the second intumescent layer are both subjected to heat.
[0019] The present disclosure also teaches a system for fireproofing an opening in an otherwise fireproofed door. The system has means for supporting longitudinally extending slats in the opening; and means disposed within the slats for expanding under heat to form an airtight seal.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] With reference now to the drawings in which like numbers represent like elements throughout the several views:
[0021] FIG. 1 is a front perspective view of a door having a louver panel in both the upper door portion and the lower door portion;
[0022] FIG. 2 is front elevational view of a louver panel according to the present disclosure;
[0023] FIG. 3 is a schematic side elevational view showing the spacing and details of the louver slats;
[0024] FIG. 4 is an enlarged cross-sectional view of one of the louvers according to the present disclosure;
[0025] FIG. 5 is an enlarged perspective view of two seated louvers; and
[0026] FIG. 6 is an enlarged cross-sectional view of a second aspect of a louver panel in accordance with the present disclosure.
DETAILED DESCRIPTION
[0027] A louvered door 10 according to the present disclosure is depicted in FIG. 1 . Door 10 comprises a frame 12 , a door knob 14 , and upper and lower louver panels 16 and 18 , respectively, in accordance with the present disclosure. It is noted, however, that a louver panel may be placed in only the bottom of the door (as is traditionally done), in the top of the door, in both the bottom and top of the door, or any other region of the door. Door 10 can be made of any contemporary material such as wood, metal, plastic or fiber board. Further, door 10 can be of any style, such as the door depicted in FIG. 1 , or a panel door, or any other kind of door.
[0028] Louver panels 16 and 18 as shown are identical, and thus only panel 16 will be discussed further. As shown in FIG. 2 , panel 16 is comprised of a circumferential frame 20 and a bisecting vertical mid-support member 22 . Frame 20 has an upper and a lower board 24 and 26 , and a left and a right end board 28 and 30 that are rigidly, fixedly attached at their respective ends to the adjacent boards so as to form a unitary, rigid, rectangular, hollow frame. Mid-support member 22 has a number of openings (not shown) which extend completely through it in the longitudinal direction. Through each opening there is a longitudinally extending slat 32 that is embedded at each end thereof in corresponding openings in end boards 28 and 30 . Slats are rigidly fixed in end boards 28 and 30 in a conventional way, such as one or more of an adhesive or a mechanical fastener, such as nails, pins, staples, screws, and dowels. Alternatively, they can just be force-fitted into an appropriately sized opening 34 . Although slats 32 are depicted as being flat, they could also have an inverted “V” shape with equal length arms or different length arms, or be any other slat shape known in the art, so long as room is provided for expansion of the slat in at least one dimension, as will be described below.
[0029] Frame 20 is preferably made out of a good quality hardwood, such as oak, or maple, but it could also be made from High Density Fiberboard (HDF) or Medium Density Fiberboard (MDF) materials and covered with a veneer. In addition, frame 20 could be made of a metal or plastic material. An exemplary dimension of mid-support member 22 is a width of a quarter of an inch (0.25″) and a length that can vary with the design of louver 16 , but in FIG. 2 is 11.5 inches. Exemplary dimensions of top and bottom boards 24 and 26 members are a length of twenty-four inches and a thickness of a quarter of an inch. The width of member 22 and boards 24 , 26 , 28 and 30 are usually the same, varying with the thickness of door 10 , but are usually one inch to two inches. In FIG. 3 , board 30 may, as a non-limiting example, be 1.75 inches wide. Slats 32 are usually set at an angle with the horizontal so that one cannot see through door 10 . In FIG. 3 , this angle is sixty degrees (601) and the spacing or distance along a vertical line, such as line 36 , is 0.5 inches. Another popular angle of slats 32 is forty degrees (401), in which case the vertical spacing along a vertical line would be 0.653 inches. However, they could also be parallel to upper and lower boards 24 and 26 (that is, perpendicular to the plane of the door), as in the case when louver 16 is in a window opening. Slats 32 may be given a length of exactly that of frame 16 if they extend completely through end boards 28 and 30 , or a few sixteenths of an inch less if they do not, or any other necessary length. Slats 32 have an exemplary thickness of a quarter of an inch (0.25″) and a spacing of 0.125 inches, but as explained below, the spacing can vary depending upon the constitution of slat 32 and on any intumescent material therein. For example, in FIG. 3 , slats 32 have a spacing of a quarter of an inch (0.250″). The length of slats 32 in FIG. 3 is 1.75 inches, but that length will vary with the angle and the thickness of frame 20 . As shown in FIG. 4 , each slat 32 comprises a shell 40 and an inner stuffing 42 . Shell 40 completely surrounds stuffing 42 on five sides, but is open on one side. Shell 40 is preferably made of a hardwood, but could be made of a metal material, such as steel, or a plastic material. Such a plastic material, if used in a fire door, must be carefully chosen so as not to melt in a hot fire. This is also true of member 22 and boards 24 , 26 , 28 and 30 . Shell has an exemplary external length of 1.750 inches and an exemplary overall thickness of 0.25 inches. As shown in FIG. 4 , slat 32 has an inner cavity 44 in which stuffing 42 is contained. Inner cavity 44 has an exemplary length of 1.5 inches and thickness of 0.1875 inches. Thus, the thickness of shell 40 along the top thereof (as depicted in FIG. 4 ) is 0.0625 inches.
[0030] Stuffing 42 is preferably made of an appropriate intumescent material. This material expands when heated above a known temperature in one direction if the other directions are confined. A relatively large expansion force and impulse may be provided, depending upon the rate of expansion, which quickly and effectively seals the spaces between (and/or around) the slats. The distance of the expansion depends upon the material and the thickness of the material, as well as the shell material.
[0031] Making reference again to FIG. 2 , when louver panel 16 is subjected to heat, the intumescent material will expand and contact the adjacent slat, thereby forming an airtight seal. The spacing between slats and the type and thickness of the intumescent material are all selected to properly provide this seal. The top slat in panel 16 is sealed with upper board 24 and thus all of the expansions between slats occur in a downward direction. This is merely one example, however, the expansion may occur upwards, or both upwards and downwards, or in any other direction necessary to form a seal.
[0032] FIG. 5 depicts an aspect of an opening 34 in an end board 30 into which one or more louvers 32 may be seated. The end board 30 may be configured to allow the louvers 32 to move at an operator=s request, or when subjected to forces caused by expansion of the intumescent material. The end board 30 may alternatively hold the louvers 32 at a rigid angle, thereby helping direct any expansion of the intumescent material into place for forming a seal. FIG. 6 depicts an alternative aspect of a slat 50 . Slat 50 comprises an outer skin or layer 52 , which may be made of a shrinkwrap or other veneer wrapping material, as is well known in the industry. Inside are upper and lower (as depicted in the figure) layers 54 and 56 , made of HDF, or another structural material such as (as non-limiting examples) wood or MDF. In between layers 54 and 56 is a layer 58 of an intumescent material, such as described above.
[0033] In addition, strips of the intumescent material can be inserted in other parts of the louver door, such as on its edges so as to seal the space between the door and the door frame. Similarly, intumescent material can be used in the frame work. In either case, the material can be attached by conventional methods, such as gluing strips of the material into a solid wooden piece or may be inserted into a veneer and wrapped by HDE or MDE as described above. The presently disclosed louvers may be used in a variety of environments, including (as non-limiting examples) gratings and ventilation ducts; wooden or steel single-leaf or multi-leaf doors, with or without glazing; sliding doors, rolling gates; sound-insulation doors, functioning in the event of a fire at the same time as a fire and smoke doors, for hospitals, schools, hotels, and office buildings; doors with high mechanical stability for industrial construction; enhanced heat-insulating sliding doors for cold-storage rooms; elevator doors; doors on ships; and steel closures for fuel oil or other combustible material storerooms.
[0034] The presently disclosed apparatuses, systems, and methods may be used with many different types of louver door configurations, including (as non-limiting examples): the single flat slat type; the inverted “V” type; and the type that has slats going in one direction on one door side, a central opening, and slats slanting in the other direction on the other door side. The present disclosure may be used with fixed slats or with slats of the adjustable or jalousie type. Portions of the louvers may be made from wood, metal, such as iron, steel, or aluminum, or plastic, such as those to which Ohanesian U.S. Pat. No. 5,778,598, is drawn, for example, which depicts a jalousie shutter door assembly assembled primarily from extruded plastic components.
[0035] The previous description of some aspects is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these aspects will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other aspects without departing from the spirit or scope of the invention. For example, one or more elements can be rearranged and/or combined, or additional elements may be added. Thus, the present invention is not intended to be limited to the aspects shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein. | A fireproof louver panel includes a panel frame and a plurality of longitudinally extending slats attached to the panel frame. One or more of the slats has a shell and an intumescent layer that expands under heat to form an airtight seal. A fireproof door or window may include an external frame, an internal core of a fireproof material (among other materials), and one or more such fireproof louver panels. A method of fireproofing an opening includes affixing a movable fireproof closure in the opening, and placement intumescent layers on the closure and on louvers disposed therein so that the opening is sealed when the first intumescent layer and the second intumescent layer are both subjected to heat. | 4 |
TECHNICAL FIELD
[0001] The present invention relates to an input support device for presenting candidates for a search keyword only by inputting a phonetic rendering by a several characters in order to efficiently input a keyword for a search or the like in equipment such as a car navigation system or a display device for FA.
BACKGROUND ART
[0002] With the advance of various kinds of electronic equipment having higher functionalities, needs for viewing/searching of electronic manuals and the like on the equipment have grown. Further, from the aspect of environmental issues, needs for converting a conventional paper manual into an electronic format are large. In addition, a search function is essential in the equipment that uses a vast amount of content for a facility name search in destination setting of a car navigation system. However, there is a problem that the equipment including no keyboard makes it difficult to input a keyword for a search and requires time and labor in operation, thereby failing to sufficiently making use of a digitized document on the equipment. Therefore, as a technology for reducing the time and labor in input operation, JP 2008-242817 A entitled “Character input device and character input program” (Patent Literature 1) discloses a technology capable of improving efficiency of character input operation by predicting a desired character string to be continuously input by a user based on a character input by the user and screening prediction candidates based on the already-input character.
CITATION LIST
Patent Literature
[0003] [PTL 1]: JP 2008-242817 A entitled “Character input device and character input program”
SUMMARY OF INVENTION
Technical Problem
[0004] However, according to the conventional Patent Literature 1, no consideration is given to ambiguity of a word break. Therefore, in a case where a break pattern of a word which is registered in a phrase dictionary built into the electronic equipment differs from a break pattern of the word which is employed when a user inputs the word, there has been a problem in that a candidate intended by the user, in other words, the word with the break pattern employed by the user inputting the word, is not registered in the phrase dictionary, which requires time and labor in the inputting. For example, in a case of inputting “KANAZAWAHAKKEISOUGOUHOKENJIMUSHO”, which is registered as “KANAZAWAHAKKEI/SOUGOUHOKENJIMUSHO” in the phrase dictionary, as a destination of the car navigation system, even when the user attempts to input the phrase in chunks: “KANAZAWA/HAKKEI/SOUGOU/HOKENJIMUSHO”, no predictive conversion is performed if the break “KANAZAWA/HAKKEI” is not included in the phrase dictionary, which necessitates the inputting using another means such as kana-kanji conversion. An intended predictive conversion result is obtained if all those break patterns are registered in the phrase dictionary, but there are enormous combinations thereof, and hence the phrase dictionary becomes extremely large and hard to be built into normal electronic equipment.
[0005] Further, according to the conventional Patent Literature 1, no consideration is given to a phrase exhibiting ambiguity in part of its representation. Therefore, in a case where the user selects a representation different from a representation of a word registered in the phrase dictionary, there is a problem in that a predictive conversion result intended by the user is not obtained. For example, in a case of inputting “YOKOHAMAAISUKOUBOU” as the destination of the car navigation system, there is a problem in that the predictive conversion is not performed for “AISUKOUBOU” when the user erroneously selects the candidate “YOKOHAMA”.
[0006] The present invention has been made in order to solve the problems as described above, and an object thereof is to improve operability in predictive conversion by considering ambiguity of a word break in the predictive conversion to present prediction candidates expected by a user even if a break pattern of a word which is registered in a dictionary differs from a break pattern of the word which is employed when the user inputs the word.
[0007] Another object thereof is to improve the operability by considering a phrase exhibiting ambiguity in part of its representation to present a predictive conversion result intended by the user even in a case where the user selects a representation different from a representation of a word registered in the dictionary.
Solution to Problem
[0008] According to the present invention, there is provided an input support device, which presents, when a phonetic rendering is input, words of a predictive keyword, which is obtained by separating a keyword that starts with the phonetic rendering by a word break, as candidates in units of breaks and which allows the keyword to be input hierarchically while selecting presented candidate words, the input support device including:
[0009] input means for receiving a phonetic rendering character string input by a user or a selection result of a presentation candidate word;
[0010] storage means in which the input means records the input phonetic rendering character string or the selection result of the presentation candidate word, which have been received, as a phonetic rendering character string;
[0011] a keyword dictionary including a phonetic rendering, a break of the phonetic rendering, a representation corresponding to the phonetic rendering, and a break of the representation corresponding to the break of the phonetic rendering;
[0012] candidate search means for searching, based on a phonetic rendering input by the user, the storage means for a phonetic rendering character string that follows the input phonetic rendering, and searching the keyword dictionary for presentation candidates based on the retrieved phonetic rendering character string;
[0013] word break matching candidate generation means for generating a presentation candidate list whose word break matches the selection result selected by the user in process of screening candidates based on search results from the candidate search means;
[0014] word break matching candidate count determination means for determining whether or not a number of elements within the presentation candidate list generated above is less than a maximum number of candidates that can be displayed on a screen;
[0015] word break mismatching candidate generation means for extracting, when a result from the word break matching candidate count determination means is less than the maximum number of candidates that can be displayed, a keyword candidate whose phonetic rendering matches that of the selection result selected by the user in the process of screening the candidates even if the word break differs therefrom, adding the keyword candidate to a word break matching presentation candidate list to generate the presentation candidate list; and
[0016] candidate display means for displaying the presentation candidate list,
[0017] in which the candidate search means further selects a candidate word from the presentation candidate list displayed by the candidate display means, and stores the candidate word in the storage means.
[0018] According to the present invention, there is provided another input support device, which presents, when a phonetic rendering is input, words of a predictive keyword, which is obtained by separating a keyword that starts with the phonetic rendering by a word break, as candidates in units of breaks and which allows the keyword to be input hierarchically while selecting presented candidate words, the input support device including:
[0019] input means for receiving a phonetic rendering character string input by a user or a selection result of a presentation candidate word;
[0020] storage means in which the input means records the input phonetic rendering character string or the selection result of the presentation candidate word, which have been received, as a phonetic rendering character string;
[0021] a keyword dictionary including a phonetic rendering, a break of the phonetic rendering, a representation corresponding to the phonetic rendering, and a break of the representation corresponding to the break of the phonetic rendering;
[0022] candidate search means for searching, based on a phonetic rendering input by the user, the storage means for a phonetic rendering character string that follows the input phonetic rendering, and searching the keyword dictionary for presentation candidates based on the retrieved phonetic rendering character string;
[0023] representation matching candidate generation means for generating a presentation candidate list whose representation matches the selection result selected by the user in process of screening candidates based on search results from the candidate search means;
[0024] representation matching candidate count determination means for determining whether or not a number of elements within the presentation candidate list generated above is less than a maximum number of candidates that can be displayed on a screen;
[0025] representation mismatching candidate generation means for extracting, when a result from the representation matching candidate count determination means is less than the maximum number of candidates that can be displayed, a presentation candidate whose phonetic rendering matches that of the selection result selected by the user in the process of screening the candidates but whose representation of the word partially differs therefrom, extracting words following the selection result in a score order, adding the words to a representation matching presentation candidate list to generate the presentation candidate list; and
[0026] candidate display means for displaying the presentation candidate list,
[0027] in which the candidate search means further selects a candidate word from the presentation candidate list displayed by the candidate display means, and stores the candidate word in the storage means.
Advantageous Effects of Invention
[0028] An input support device according to the present invention has a configuration in which: a phonetic rendering character string input by a user or a selection result of a presentation candidate is received through input means and stored in storage means; candidate search means searches a keyword dictionary for a presentation candidate by using a phonetic rendering based on the input or the selected presentation candidate, the keyword dictionary including a phonetic rendering, a break of the phonetic rendering, a representation corresponding to the phonetic rendering, and a break of the representation corresponding to the break of the phonetic rendering; word break matching candidate generation means generates a presentation candidate list whose word break matches the selection result in process of screening candidates based on search results; word break matching candidate count determination means determines whether or not the number of elements within the presentation candidate list is less than a maximum number that can be displayed; word break mismatching candidate generation means extracts, when a result thereof is less, a candidate whose phonetic rendering matches that of the selection result in the process of screening the candidates but whose word break differs therefrom, cuts out a representation character string following the selection result in the process of the screening from within the representation character string of the same candidate, and adds the cut-out representation character string to the presentation candidate list; and display means displays the presentation candidate list. Accordingly, when the phonetic rendering matches even if the word break differs from that of the keyword dictionary, the candidate display means presents the word as the presentation candidate list, and hence it is possible to obtain the effect that the operability in the predictive conversion can be improved by presenting the prediction candidates expected by the user even if the break pattern of the word at the time when the user inputs the word differs from the break pattern of the word registered in the dictionary.
[0029] Further, another input support device according to the present invention has a configuration in which: a phonetic rendering character string input by a user or a selection result of a presentation candidate is received through input means and stored in storage means; candidate search means searches a storage unit for a phonetic rendering character string following the input phonetic rendering, and searches a keyword dictionary for a presentation candidate based on the phonetic rendering character string, the keyword dictionary including a phonetic rendering, a break of the phonetic rendering, a representation corresponding to the phonetic rendering, and a break of the representation corresponding to the break of the phonetic rendering; representation matching candidate generation means generates a presentation candidate list whose representation matches the selection result selected by the user in process of screening candidates based on search results; representation mismatching candidate generation means extracts in a score order, when it is determined by representation matching candidate count determination means that the number of elements within the presentation candidate list is less than a maximum number of candidates that can be displayed on a screen, presentation candidates whose phonetic renderings match that of the selection result in the process of screening the candidates but whose representations of the words partially differ therefrom, and adds the presentation candidates to a representation matching presentation candidate list to generate the presentation candidate list; and candidate display means displays the presentation candidate list, to thereby consider the phrase exhibiting the ambiguity in part of its representation. Accordingly, it is possible to obtain the effect that the operability can be improved by presenting the predictive conversion result intended by the user even in the case where the user selects the representation different from the representation of the word registered in the keyword dictionary (for example, “YOKOHAMA/AISUKOUBOU”) with respect to (“YOKOHAMA/AISUKOUBOU”).
BRIEF DESCRIPTION OF DRAWINGS
[0030] [ FIG. 1 ] A basic configuration diagram according to a first embodiment of the present invention.
[0031] [ FIG. 2 ] An explanatory diagram of a facility name dictionary example.
[0032] [ FIG. 3 ] A detailed configuration diagram of a presentation candidate generation unit.
[0033] [ FIG. 4 ] An explanatory diagram of an input operation screen example (1) according to the first embodiment.
[0034] [ FIG. 5 ] A basic processing flowchart of input support processing according to the first embodiment.
[0035] [ FIG. 6 ] A detailed flowchart of the presentation candidate generation unit.
[0036] [ FIG. 7 ] An explanatory diagram of an input operation screen example (2) according to the first embodiment.
[0037] [ FIG. 8 ] An explanatory diagram of an input operation screen example ( 3 ) according to the first embodiment.
[0038] [ FIG. 9 ] A detailed configuration diagram of a presentation candidate generation unit according to a second embodiment.
[0039] [ FIG. 10 ] A detailed flowchart of a presentation candidate generation processing according to the second embodiment.
[0040] [ FIG. 11 ] An explanatory diagram of an input operation screen example (1) according to the second embodiment.
[0041] [ FIG. 12 ] An explanatory diagram of an input operation screen example (2) according to the second embodiment.
DESCRIPTION OF EMBODIMENTS
First embodiment
[0042] FIG. 1 is a basic configuration diagram according to a first embodiment of the present invention. Note that, the following description is made by taking as an example of a search for a facility name in destination setting of a car navigation system, but the present invention is not limited to the facility name search of the car navigation system, and can be applied to general equipment in which a keyword for a search is input stepwise by combining predictive conversion and phonetic rendering inputting in a search for a music track on a music player, a search through a telephone book on a cellular telephone, or other such search.
[0043] In FIG. 1 , an input unit 101 receives a phonetic rendering character string 102 input by a user and a selection result 103 of a presentation candidate from the car navigation system. Those input results are recorded in a storage unit 109 via a control unit 108 .
[0044] When there is an input of a phonetic rendering character string from the input unit 101 , a candidate search unit 104 extracts a phonetic rendering input by the user from the storage unit 109 , and searches a facility name dictionary 105 serving as a keyword dictionary to acquire facility name candidates serving as keywords that start with the phonetic rendering character string.
[0045] A presentation candidate generation unit 106 generates a presentation candidate list by extracting constituent words from the above-mentioned facility name candidates based on results selected by the user in the process of screening the candidates.
[0046] A candidate display unit 107 displays on a monitor the list generated by the presentation candidate generation unit 106 in a list format, to thereby allow the user to select a candidate.
[0047] A destination setting unit 110 sets, as a destination, the facility name selected when the user inputs a candidate determination.
[0048] FIG. 2 is an example of the facility name dictionary 105 . The facility name dictionary 105 stores data including at least “phonetic rendering ( 105 b )” and “representation ( 105 c )”, each of which includes information representing a word break. In this figure, a word break position is expressed by using a single-byte slash (/). Further, the above-mentioned data retains “score ( 105 d )” that is a numerical value indicating a priority as a prediction candidate, and the facility name that is more often used as the destination is given a higher numerical value.
[0049] FIG. 3 illustrates a detailed configuration of the presentation candidate generation unit 106 . A word break matching candidate generation unit 301 extracts N words selected by the user in the process of screening the candidates, that is, results of selecting the words separated by the word break up to the Nth word, from the storage unit 109 , extracts the facility name candidates that start with the above-mentioned N words, and extracts in the score order the (N+1)th words that have not been selected yet by the user to generate the presentation candidate list. A word break matching candidate count determination unit 302 determines whether or not the number of elements within the presentation candidate list generated by the word break matching candidate generation unit 301 exceeds the maximum number of candidates that can be displayed on a screen. A word break mismatching candidate generation unit 303 extracts the facility name whose phonetic rendering matches the N words selected by the user in the process of screening the candidates even if the word break differs therefrom, cuts out a representation character string following the selection result in the process of the screening from within the representation character string of the same candidate, and adds the cut-out representation character string to the presentation candidate list.
[0050] Reference numeral 401 of FIG. 4 indicates an example of an operation screen constituting the input unit 101 and the candidate display unit 107 , for performing the phonetic rendering inputting and candidate selection through the software keyboard, a numeric keypad, and the like displayed on a touch panel screen. Reference numeral 402 denotes a display portion for displaying the phonetic rendering input by the user and the candidate selection result. Reference numeral 403 denotes a numeric keypad group for inputting the phonetic rendering, on which, for example, each time a “KA” column key 404 is touched, the phonetic rendering is converted in order of the KA column as in “KA”→“KI”→“KU”→“KE”→“KO”. Reference numeral 405 denotes a predictive conversion candidate display area portion for displaying a predictive conversion candidate, which, if a candidate desired by the user is displayed, allows selection thereof by a touch on the corresponding one of individual candidate buttons 406 . A destination setting button 407 is used for setting the facility name selected by the user as the destination. Note that, the phonetic rendering inputting and the candidate selection that are performed by direct operations on the screen through the touch panel are taken as examples above, but the selection and the operation may be performed on the item displayed on the screen by using remote control keys or operation keys equipped in a main body. Further, FIG. 4 illustrates the example in which five candidates are presented at maximum, but a scrollbar or a page skip key may be provided to thereby allow 10 or more candidates to be presented at maximum.
[0051] Hereinafter, a description is made of processing contents of the present invention by referring to FIGS. 1 to 8 appropriately. The description is made by assuming that the user is attempting to set “KANAZAWAHAKKEIEKI” as the destination in the car navigation system.
[0052] FIG. 5 is a basic processing flow of the input support device according to the present invention. In FIG. 5 , Step ST 1 denotes processing for inputting a phonetic rendering or selecting a presentation candidate. Immediately after a start of input support processing, in other words, in Step ST 1 in an initial state, the input unit 101 receives the phonetic rendering character string 102 of the keyword for a search input by the user. Here, “KA” is assumed to have been input as illustrated in the display portion 402 of FIG. 4 .
[0053] Step ST 2 denotes input end determination processing, in which the control unit 108 determines whether or not a destination setting key ( 407 of FIG. 4 ) has been operated. If operated, the control unit 108 determines that the inputting has been finished, and if not, executes processing of Step ST 3 and the subsequent steps. Here, the phonetic rendering “KA” has been input, and hence the procedure advances to Step ST 3 and the subsequent steps.
[0054] Step ST 3 denotes presentation candidate search processing, in which the candidate search unit 104 searches the facility name dictionary 105 for the facility names that start with the input phonetic rendering character string “KA”. In the case of the facility name dictionary illustrated in FIG. 2 , R 1 to R 15 and the like are retrieved as the facility name candidates. Note that, although not illustrated in FIG. 2 , a large number of facility names that start with “KANAGAWA”, “KAMAKURA”, “KAWASAKI”, and “KATASE” are assumed to be registered in positions of/after R 23 .
[0055] Step ST 4 denotes presentation candidate generation processing, in which the presentation candidate generation unit 106 generates the presentation candidate list by extracting the constituent words from R 1 to R 15 retrieved from the facility name dictionary 105 by the candidate search unit 104 , based on the results selected by the user in the process of screening the candidates.
[0056] FIG. 6 illustrates a detailed flow of the presentation candidate generation processing. In FIG. 6 , Step ST 601 denotes word break matching candidate generation processing, in which the word break matching candidate generation unit ( 301 of FIG. 3 ) extracts the N words, which are the results selected by the user in the screening of the candidates, from the storage unit 109 , extracts the facility name candidates that start with the above-mentioned N words, and extracts in the score order the (N+1)th words that have not been selected yet by the user to generate the presentation candidate list. Here, the user has just input the first character of the phonetic rendering and candidate screening results do not exist yet, and hence the first words of the representations of the facility names in the highest positions of the “score” ( 105 c of FIG. 2 ) are extracted from among all the facility name candidates. Here, five candidates including “KANAGAWA”, “KAMAKURA”, “KAWASAKI”, and “KATASE” are generated as the presentation candidate list.
[0057] Step ST 602 denotes word break matching candidate count determination processing, in which the word break matching candidate count determination unit ( 302 of FIG. 3 ) determines whether or not the number of elements within the presentation candidate list generated above exceeds the maximum number of candidates that can be displayed on the screen. Here, the maximum number of candidates that can be displayed on the screen is five with a word break matching candidate count being five or more, and hence the presentation candidate generation processing is finished without advancing to Step ST 603 (described later).
[0058] Step ST 5 of FIG. 5 denotes candidate display processing, in which the candidate display unit 107 displays the presentation candidate list generated above. Reference numeral 405 of FIG. 4 indicates a state in which those candidates are presented.
[0059] Subsequently, the procedure returns to Step ST 1 to receive an input from the user. Here, the user is attempting to set “KANAZAWAHAKKEIEKI” as the destination, and hence selects “KANAZAWA” by using the candidate presentation button 406 of FIG. 4 . In Step ST 2 , it is determined that the inputting has not been finished because there is no operation of the destination setting button ( 407 of FIG. 4 ), and the procedure advances to Step ST 3 .
[0060] In Step ST 3 , the candidate search unit 104 searches the facility name dictionary 105 for the facility names that start with the candidate “KANAZAWA” selected by the user. In the case of the facility name dictionary illustrated in FIG. 2 , R 4 to R 13 are retrieved as the facility name candidates.
[0061] Subsequently, in Step ST 4 , based on “KANAZAWA” selected by the user in the screening of the candidates, the presentation candidate generation unit 106 generates the presentation candidate list by extracting the constituent words from R 4 to R 13 retrieved from the facility name dictionary 105 . With regard to the presentation candidate generation processing, a description is made of an operation thereof by referring to the detailed flow of FIG. 6 . Step ST 601 denotes the word break matching candidate generation processing, in which the word break matching candidate generation unit ( 301 of FIG. 3 ) extracts the N words (here, N=1), which are the results selected by the user in the screening of the candidates, from the storage unit 109 , extracts the facility name candidates that start with the above-mentioned N words, and extracts in the score order the (N+1)th words that have not been selected yet by the user to generate the presentation candidate list. Here, the candidates are screened to R 4 to R 10 as the candidates in which “KANAZAWA” selected by the user is the first word, from among which the second words of the representations of the facility names in the highest positions of the “score” ( 105 c of FIG. 2 ) are extracted. Here, five elements including “KUYAKUSHO”, “KOUKAIDOU”, “CHIKUSENTAA”, “SUPOOTSUSENTAA”, and “TOSHOKAN” are generated as the presentation candidate list.
[0062] Step ST 602 denotes the word break matching candidate count determination processing, in which the word break matching candidate count determination unit ( 302 of FIG. 3 ) determines whether or not the number of elements within the presentation candidate list generated above exceeds the maximum number of candidates that can be displayed on the screen. Here, the maximum number of candidates that can be displayed on the screen being five is equal to the number of elements, and hence the presentation candidate generation processing is finished without advancing to Step ST 603 (described later).
[0063] Step ST 5 of FIG. 5 denotes the candidate display processing, in which the candidate display unit 107 displays the presentation candidate list generated above. The display area portion 405 of FIG. 7 indicates a state in which those candidates are presented.
[0064] Subsequently, the procedure returns to Step ST 1 to receive an input from the user. Here, the user is attempting to set “KANAZAWAHAKKEIEKI” as the destination, and hence inputs “HA” by using a phonetic rendering input key 403 of FIG. 8 . In Step ST 2 , it is determined that the inputting has not been finished because there is no operation of the destination setting button ( 407 of FIG. 8 ), and the procedure advances to Step ST 3 .
[0065] In Step ST 3 , the candidate search unit 104 searches the facility name dictionary 105 for the facility names that start with the input phonetic rendering character string, here, “KANAZAWAHA” obtained by adding the further input phonetic rendering “HA” to the phonetic rendering “KANAZAWA” of the candidate “KANAZAWA” selected by the user. In the case of the facility name dictionary illustrated in FIG. 2 , R 9 to R 13 are retrieved as the facility name candidates.
[0066] Subsequently, in Step ST 4 , based on “KANAZAWA” selected by the user in the screening of the candidates, the presentation candidate generation unit 106 generates the presentation candidate list by extracting the constituent words from the facility name candidates R 9 to R 13 retrieved from the facility name dictionary 105 . A description is made of an operation thereof by referring to the detailed flow of the presentation candidate generation processing of FIG. 6 . Step ST 601 denotes the word break matching candidate generation processing, in which the word break matching candidate generation unit ( 301 of FIG. 3 ) extracts the N words, which are the results selected by the user in the screening of the candidates, from the storage unit 109 , extracts the facility name candidates that start with the above-mentioned N words, and extracts in the score order the (N+1)th words that have not been selected yet by the user to generate the presentation candidate list. Here, the facility name candidates R 9 and R 10 are extracted as the candidates in which “KANAZAWA” selected by the user is the first word. As a result, the second words of those representations are extracted to generate “HAISOUSENTAA” and “HAITEKUSENTAA” as the presentation candidate list.
[0067] Step ST 602 denotes word break matching candidate count determination processing, in which the word break matching candidate count determination unit ( 302 of FIG. 3 ) determines whether or not the number of elements within the presentation candidate list generated above exceeds the maximum number of candidates that can be displayed on the screen. Here, the maximum number of candidates that can be displayed on the screen is five with the number of elements being two, and hence the procedure advances to Step ST 603 .
[0068] Step ST 603 denotes word break mismatching candidate generation processing, in which the word break mismatching candidate generation unit ( 303 of FIG. 3 ) extracts the facility name candidates whose phonetic rendering matches the N words selected by the user in the process of screening the candidates even if the word break differs therefrom, cuts out a representation character string following the selection result in the process of the screening from within the representation character string of the same candidate, and adds the cut-out representation character string to the presentation candidate list. Here, the facility names R 11 , R 12 , and R 13 are extracted. “HAKKEIEKI” obtained by excluding “KANAZAWA” from the representation of the leading word of R 11 is added to the presentation candidate list, and “HAKKEI” obtained by excluding “KANAZAWA” from the leading word of R 12 and R 13 is also added to the presentation candidate list. The presentation candidate generation processing is finished here, and the procedure advances to the subsequent step (ST 5 of FIG. 5 ).
[0069] Step ST 5 of FIG. 5 denotes candidate display processing, in which the candidate display unit 107 displays the presentation candidate list generated above. Reference numeral 405 of FIG. 8 indicates a state in which those candidates are presented. In addition, the procedure returns to Step ST 1 , in which the user selects “HAKKEIEKI” ( 406 of FIG. 8 ). In addition, after repeating the processing from Step ST 2 to Step ST 5 , the user operates “SET DESTINATION” ( 407 of FIG. 8 ) again in Step ST 1 , and the input support processing is finished after Step ST 2 .
[0070] As described above, it is possible to obtain an effect that operability in predictive conversion can be improved by considering ambiguity of a word break in the predictive conversion to present the prediction candidates expected by the user even if the break pattern of the word (“KANAZAWAHAKKEIEKI” without a break) which is registered in the dictionary differs from the break pattern of the word (“KANAZAWA/HAKKEIEKI”) which is employed when the user inputs the word.
Second Embodiment
[0071] FIG. 9 is a detailed configuration diagram of the presentation candidate generation unit 106 according to a second embodiment of the present invention. A representation matching candidate generation unit 901 extracts results of selecting N words selected by the user in the process of screening the candidates from the storage unit 109 , extracts the facility name candidates that start with the above-mentioned N words, and extracts in the score order the (N+1)th words that have not been selected yet by the user to generate the presentation candidate list. A representation matching candidate count determination unit 902 determines whether or not the number of elements within the presentation candidate list generated above exceeds the maximum number of candidates that can be displayed on a screen. A representation mismatching candidate generation unit 903 extracts the facility name candidates whose phonetic rendering matches the N words selected by the user in the process of screening the candidates but whose representation of the word partially differs therefrom, extracts in the score order the (N+1)th words that have not been selected yet by the user, and adds the extracted (N+1)th words to the presentation candidate list. The other configuration is the same as that of the first embodiment, and hence the descriptions of the other means are omitted.
[0072] FIG. 10 illustrates a detailed flow of presentation candidate generation processing according to the second embodiment of the present invention. The other steps are the same as those of the first embodiment, and hence details thereof are omitted. Hereinafter, a description is made of processing contents of the second embodiment of the present invention by referring to FIG. 1 , FIG. 2 , FIG. 5 , and FIG. 9 to FIG. 12 appropriately. The description is made by assuming that the user is attempting to set “YOKOHAMAAISUKOUBOU” as the destination. Immediately after the start of the input support processing, in other words, in Step ST 1 ( FIG. 5 ) in the initial state, the input unit 101 receives the phonetic rendering character string 102 of the keyword for a search input by the user. Here, “YO” is assumed to have been input as illustrated in the display portion 402 of FIG. 11 .
[0073] Step ST 2 ( FIG. 5 ) denotes the input end determination processing, in which the control unit 108 determines whether or not the destination setting key ( 407 of FIG. 11 ) has been operated. If operated, the control unit 108 determines that the inputting has been finished, and if not, executes the processing of Step ST 3 and the subsequent steps. Here, the phonetic rendering “YO” has been input, and hence the procedure advances to Step ST 3 and the subsequent steps.
[0074] Step ST 3 denotes the presentation candidate search processing, in which the candidate search unit 104 searches the facility name dictionary 105 for the facility names that start with the input phonetic rendering character string “YO”. In the case of the facility name dictionary illustrated in FIG. 2 , R 16 to R 22 are retrieved as the facility name candidates.
[0075] Step ST 4 denotes the presentation candidate generation processing, in which the presentation candidate generation unit 106 generates the presentation candidate list by extracting the constituent words from R 16 to R 22 retrieved from the facility name dictionary 105 by the candidate search unit 104 , based on the results selected by the user in the process of screening the candidates. Step ST 1001 of FIG. 10 denotes representation matching candidate generation processing, in which the representation matching candidate generation unit ( 901 of FIG. 9 ) extracts the N words being the results selected by the user in the screening of the candidates from the storage unit 109 , extracts the facility name candidates that start with the above-mentioned N words, and extracts in the score order the (N+1)th words that have not been selected yet by the user to generate the presentation candidate list. Here, the user has just input the first character of the phonetic rendering and the candidate screening results do not exist yet, and hence the first words of the representations of the facility names in the highest positions of the “score” ( 105 c of FIG. 2 ) are extracted from among all the facility name candidates. Here, “YOKOHAMA”, “YOKOHAMA”, and “YOKOHAMA” are generated from R 16 to R 22 as the presentation candidate list.
[0076] Step ST 1002 denotes representation matching candidate count determination processing, in which the representation matching candidate count determination unit ( 902 of FIG. 9 ) determines whether or not the number of elements within the presentation candidate list generated above is equal to or larger than the maximum number of candidates that can be displayed on the screen. Here, the maximum number of candidates that can be displayed on the screen is five with the number of elements being three, and hence the procedure advances to Step ST 1003 .
[0077] Step ST 1003 denotes representation mismatching candidate generation processing, in which the representation mismatching candidate generation unit ( 903 of FIG. 9 ) extracts the facility name candidates whose phonetic rendering matches the N words selected by the user in the process of screening the candidates but whose representation of the word partially differs therefrom, extracts in the score order the (N+1)th words that have not been selected yet by the user, and adds the extracted (N+1)th words to the presentation candidate list. Here, the user has just input the first character of the phonetic rendering without the existence of the candidate screening results, and hence there is no addition to the presentation candidate list in this step because the first words are extracted as the presentation candidate list from all the facility name candidates in Step ST 1001 . The presentation candidate generation processing is finished here, and the procedure advances to the subsequent step (ST 5 of FIG. 5 ).
[0078] Step ST 5 of FIG. 5 denotes candidate display processing, in which the candidate display unit 107 displays the presentation candidate list generated above. Reference numeral 405 of FIG. 11 indicates a state in which those candidates are presented.
[0079] Subsequently, the procedure returns to Step ST 1 to receive an input from the user. Here, it is assumed that the user is attempting to set “YOKOHAMAAISUKOUBOU” as the destination but has selected “YOKOHAMA” ( 406 of FIG. 11 ) without noticing that the formal name is “YOKOHAMA”. In Step ST 2 , it is determined that the inputting has not been finished because there is no operation of the destination setting button ( 407 of FIG. 11 ), and the procedure advances to Step ST 3 .
[0080] In Step ST 3 , the candidate search unit 104 searches the facility name dictionary 105 for the facility names that start with the input phonetic rendering character string, here, the phonetic rendering “YOKOHAMA” of “YOKOHAMA” selected by the user. In the case of the facility name dictionary illustrated in FIG. 2 , R 16 to R 22 are retrieved as the facility name candidates.
[0081] Subsequently, in Step ST 4 , based on “YOKOHAMA” selected by the user in the screening of the candidates, the presentation candidate generation unit 106 generates the presentation candidate list by extracting the constituent words from R 16 to R 22 retrieved from the facility name dictionary. A description is made of an operation thereof by referring to the detailed flow of the presentation candidate generation processing of FIG. 10 . Step ST 1001 denotes the representation matching candidate generation processing, in which the representation matching candidate generation unit ( 901 of FIG. 9 ) extracts the N words being the results selected by the user in the screening of the candidates from the storage unit 109 , extracts the facility name candidates that start with the above-mentioned N words, and extracts in the score order the (N+1)th words that have not been selected yet by the user to generate the presentation candidate list. Here, the candidates are screened to R 16 to R 18 as the candidates in which “YOKOHAMA” selected by the user is the first word, from among which the second words of the representations of the facility names in the highest positions of the “score” ( 105 c of FIG. 2 ) are extracted. Here, “SHIYAKUSHO”, “SHIRITSU”, and “SEIKASENTAA” are generated as the presentation candidate list.
[0082] Step ST 1002 denotes representation matching candidate count determination processing, in which the representation matching candidate count determination unit ( 1002 of FIG. 10 ) determines whether or not the number of elements within the presentation candidate list generated above is smaller than the maximum number of candidates that can be displayed on the screen. Here, the maximum number of candidates that can be displayed on the screen is five with the number of elements being three, and hence the procedure advances to Step ST 1003 .
[0083] Step ST 1003 denotes representation mismatching candidate generation processing, in which the representation mismatching candidate generation unit ( 903 of FIG. 9 ) extracts the facility name candidates whose phonetic rendering matches the N words selected by the user in the process of screening the candidates but whose representation of the word partially differs therefrom, extracts in the score order the (N+1)th words that have not been selected yet by the user, and adds the extracted (N+1)th words to the presentation candidate list. Here, the facility names of R 19 to R 22 are extracted, and “GURANDO, “AISUKOUBOU”, “KARAOKEGAKUIN”, and “BUNMEIKAIKAN” being the second words thereof are added to the presentation candidate list in the score order. The presentation candidate generation processing is finished here, and the procedure advances to the subsequent step (ST 5 of FIG. 5 ).
[0084] Step ST 5 of FIG. 5 denotes candidate display processing, in which the candidate display unit 107 displays the presentation candidate list generated above. The display area portion 405 of FIG. 12 indicates a state in which those candidates are presented. In addition, the procedure returns to Step ST 1 , in which the user selects “AISUKOUBOU” ( 406 of FIG. 12 ). In addition, after repeating the processing from Step ST 2 to Step ST 5 , the user operates “SET DESTINATION” ( 407 of FIG. 8 ) again in Step ST 1 , and the input support processing is finished after Step ST 2 .
[0085] As described above, it is possible to obtain an effect that the operability can be improved by considering a phrase exhibiting ambiguity in part of its representation to present a predictive conversion result intended by the user even in the case where the user selects the representation (“YOKOHAMA/AISUKOUBOU”) different from the representation of the word (“YOKOHAMA/AISUKOUBOU”) registered in the dictionary.
[0086] Note that, the presentation candidate generation unit can be configured by combining both the generation of the presentation candidate list based on the matching/mismatching of the word break according to the first embodiment and the generation of the presentation candidate list based on the matching/mismatching of the representation of the word according to the second embodiment, and can be configured to perform the keyword selection processing based on the matching/mismatching of the representation of the word after the keyword selection processing based on the matching/mismatching of the word break or perform the processing by the reverse procedure. With such a configuration, it is possible to obtain an input support device for a search keyword which is capable of handling the ambiguity of the word break and the ambiguity in the representation of the word.
INDUSTRIAL APPLICABILITY
[0087] The present invention can be applied to the general equipment in which a keyword for a search is input stepwise by combining the predictive conversion and the phonetic rendering inputting. In particular, the present invention is highly effective for the facility name search of the car navigation system, the search for a music track on the music player, and the search through the telephone book on the cellular telephone, or can be highly effectively applied to the equipment including no keyboard such as a display device for FA.
REFERENCE SIGNS LIST
[0088] 101 input unit, 102 phonetic rendering character string, 103 selection result of a presentation candidate, 104 candidate search unit, 105 facility name dictionary, 106 presentation candidate generation unit, 107 candidate display unit, 108 control unit, 109 storage unit, 110 destination setting unit, 301 word break matching candidate generation unit, 302 word break matching candidate count determination unit, 303 word break mismatching candidate generation unit, 901 representation matching candidate generation unit, 902 representation matching candidate count determination unit, 903 representation mismatching candidate generation unit | An input support device, including: a keyword dictionary for storing a keyword including one or more words; a candidate search mechanism searching entries within the keyword dictionary by using a search key including one or more words specified based on a user operation; a presentation candidate generation mechanism generating a presentation candidate list based on search results from the candidate search mechanism by extracting a word break mismatching presentation candidate from the keywords whose word break does not match that of the specified search key including the one or more words and which start with the specified search key including the one or more words; and a candidate display displaying the presentation candidate list generated by the presentation candidate generation mechanism. | 6 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a divisional of U.S. patent application Ser. No. 11/408,643, filed Apr. 21, 2006, which is hereby incorporated by reference in its entirety for all purposes.
COPYRIGHT NOTICE
Contained herein is material that is subject to copyright protection. The copyright owner has no objection to the facsimile reproduction of the patent disclosure by any person as it appears in the Patent and Trademark Office patent files or records, but otherwise reserves all rights to the copyright whatsoever. Copyright© 2006-2011 Fortinet, Inc.
FIELD
Various embodiments of the present invention generally relate to systems and methods for delivering content. In particular, various embodiments relate to delivering unsolicited content, such as advertising content, to a client via a communications network such as the Internet.
BACKGROUND
Currently, advertising over the Internet is done by inserting advertisements into webpages on websites. The code for the webpage includes advertising content or one or more links to advertising servers that produce advertisements either on the webpage itself (in-line advertising) or in a separate window for the advertisement (“pop-up” or “pop-under” advertising). The types of advertisements are controlled by the content provider for the website as the advertising is built into the webpage code. However, the advertisement is limited in that the advertisement is only viewed by end-users who visit the website and run the code. In this respect, Internet advertising works much like billboards on a highway in that the advertisements are only seen by those who travel there.
This method presents two problems. First, there is no way to direct advertising to users who are not visiting a given website. The result is a smaller potential target audience for advertisers, as the audience is based on the visitors to any given website, which is a fraction of the total users on the Internet at any given time. Second, the advertising content is arranged by the content provider for the website. The Internet service provider (ISP), who is responsible for providing the bandwidth for the Internet and often the hardware for hosting the website, is not provided with a means of advertising on the Internet itself.
Thus, a need exists for systems and methods for directly targeting and directing advertisements to end users.
SUMMARY
Systems and methods are described for transmitting content to a client. According to one embodiment, a system is provided for transmitting content to a client via the Internet, the system includes a content server, an insertion server and a policy server. The content server is configured to store and select substitute or supplemental content. The insertion server is configured to monitor client traffic, detect client TCP/IP requests or destination TCP/IP responses and send the selected substitute or supplemental content retrieved from the content server to the client in lieu of or in addition to content requested by the client TCP/IP requests or provided by the destination TCP/IP responses. The policy server is configured to provide instructions to the insertion server with respect to timing of detecting the client TCP/IP requests or destination TCP/IP responses and a delay associated with completing the client TCP/IP requests or destination TCP/IP responses. The system operates independently of respective destinations of the client TCP/IP requests and respective sources of the destination TCP/IP responses.
A more complete understanding of various embodiments of the present invention may be derived by referring to the detailed description of preferred embodiments and claims when considered in connection with the figures.
BRIEF DESCRIPTION OF THE DRAWINGS
In the Figures, similar components and/or features may have the same reference label. Further, various components of the same type may be distinguished by following the reference label with a second label that distinguishes among the similar components. If only the first reference label is used in the specification, the description is applicable to any one of the similar components having the same first reference label irrespective of the second reference label.
FIG. 1 illustrates a block diagram showing the connection between a client and the Internet in accordance with one or more embodiments of the present invention;
FIG. 2 illustrates a flowchart describing a process of interpreting a client HTTP request in accordance with one or more embodiments of the present invention;
FIG. 3 illustrates a block diagram of various components of the present invention which may be used in accordance with one or more embodiments of the present invention;
FIG. 4 illustrates a flowchart describing a process of detecting and intercepting a client TCP/IP request in accordance with one or more embodiments of the present invention;
FIG. 5 illustrates a flowchart describing a process of detecting and inserting content into a TCP connection in accordance with one or more embodiments of the present invention; and
FIG. 6 illustrates an example of a computer system with which embodiments of the present invention may be utilized.
DETAILED DESCRIPTION
Various embodiments of the present invention generally relate to systems and methods for delivering content. In particular, various embodiments relate to delivering advertising content to a client via a communications network such as the Internet. In addition, various embodiments provide for systems and methods of transmitting content over a communication network to a client without the need to run code from the destination (e.g., website) selections of that client.
According to one embodiment, a system and method of transmitting content over a communications network that is capable of use and exploitation by an ISP, enterprise, and/or the like may be provided. According to one embodiment, a method may include one or more of the following steps: 1) intercepting a data transfer protocol request and/or response; 2) analyzing information contained within the intercepted data transfer protocol request/response; 3) selecting advertising content to send to the requesting/intended client; and 4) sending the selected content to the client. In one embodiment, the content may be selected based on information contained within the communication protocol request and/or response, such as information indicative of the client (e.g., an IP address used alone or as an index or key to retrieve a profile associated with the client), information indicative of the destination (e.g., an IP address used alone or as an index or key to retrieve a profile associated with the destination), the Request-URI in the HTTP request method, the Host field in the HTTP request header, the content in the response, such as the webpage content (e.g., keywords in the page).
According to various embodiments of the present invention, the systems and methods may be used at an enterprise level in order to intercept communication protocol requests/responses and deliver content, such as advertisements. For example, a hotel may provide internet service to its customers. According to one embodiment, a hotel may intercept the communication protocol requests originated by those clients using the hotel's internet service or the communication protocol responses destined for those clients using the hotel's internet service, analyze information contained within the intercepted communication protocol request/response, select advertising content to send to the client, and send the selected content to the client. According to one embodiment, a hotel may create a client profile. For example, an enterprise, such as a hotel may create a client profile by collecting and storing information about a client through a membership program, optional questionnaires, and/or the like. This information may then be accessed using the information contained within the data transfer protocol request. Then, an appropriate advertising choice may be based on the client profile. In some embodiments, no client profile is used. In this case, an enterprise, such as a hotel, may send advertisements as they become available, or on a pre-allocated basis. In one embodiment, pre-allocating an advertisement refers to determining the percentage one advertisement will be delivered in relation to other advertisements.
In one embodiment, the advertising content may be delivered via the same communications methodology used to make the request or provide the response. For example, if a client is making an HTTP request, then advertising content may be delivered via that HTTP. In some embodiments, additional information is known about the client and advertisements can be delivered via another communication method. For example, when an HTTP session is detected as active, an advertising system may send a message to the client's instant messenger while the HTTP session continues without interference.
In the following description, for the purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of embodiments of the present invention. It will be apparent, however, to one skilled in the art that embodiments of the present invention may be practiced without some of these specific details.
Embodiments of the present invention may be provided as a computer program product which may include a machine-readable medium having stored thereon instructions which may be used to program a computer (or other electronic devices) to perform a process. The machine-readable medium may include, but is not limited to, floppy diskettes, optical disks, compact disc read-only memories (CD-ROMs), and magneto-optical disks, ROMs, random access memories (RAMs), erasable programmable read-only memories (EPROMs), electrically erasable programmable read-only memories (EEPROMs), magnetic or optical cards, flash memory, or other type of media/machine-readable medium suitable for storing electronic instructions. Moreover, embodiments of the present invention may also be downloaded as a computer program product, wherein the program may be transferred from a remote computer to a requesting computer by way of data signals embodied in a carrier wave or other propagation medium via a communication link (e.g., a modem or network connection).
For the sake of illustration, various embodiments of the present invention have herein been described in the context of computer programs, physical components, and logical interactions within modern computer networks. Specifically, for convenience, embodiments of the present invention are described with reference to detecting an active session or connection by intercepting or observing TCP/IP requests over the Internet originated by clients. However, embodiments of the present invention are equally applicable to detecting an active communication protocol session or connection by intercepting or observing TCP/IP responses intended for clients.
Additionally, embodiments of the present invention are equally applicable to various other transport protocols, systems, devices, and networks as one skilled in the art will appreciate. For example, various embodiments may be used in conjunction with communications networks, such as WANs, LANs, other computer networks, telephone systems, and/or the like. More specifically, embodiments are applicable to multiple levels of implementation. For example, communication systems, services, enterprises, and devices such as cell phone networks and compatible devices. In addition, embodiments are applicable to all levels of computing from the personal computer to large network mainframes and servers. Additionally, monitoring and/or proxying of other transport communication protocol connection requests and/or responses, such as User Datagram Protocol (UDP), Datagram Congestion Control Protocol (DCCP), Stream Control Transmission Protocol (SCTP), IL, Reliable User Datagram Protocol (RUDP), AppleTalk Echo Protocol (AEP), AppleTalk Transaction Protocol (ATP), Cyclic UDP (CUDP), Name Binding Protocol (NBP), NetBIOS Extended User Interface (NetBEUI), Routing Table Maintenance Protocol (RTMP), Sequenced Packet Exchange (SPX) protocol, Network News Transport Protocol (NNTP), Real-time Transport Protocol (RTP) and/or the like, may be used in accordance with the specific communications network as known to those skilled in the art. Terminology
Brief definitions of terms, abbreviations, and phrases used throughout this application are given below.
The phrase “advertising content” generally refers to the promotion of products, services, brands, ideas, companies, and/or the like. Advertising content may be delivered in a variety of formats. Examples include, but are not limited to, pop-up advertisements, pop-under advertisements, voice advertisements, various text advertisements, and/or the like.
The phrase “communication network” or term “network” generally refers to a group of interconnected devices capable of exchanging information. A communication network may be as few as several personal computers on a Local Area Network (LAN) or as large as the Internet, a worldwide network of computers. As used herein “communication network” is intended to encompass any network capable of transmitting information from one entity to another. In one particular case, a communication network is a Voice over Internet Protocol (VoIP) network. In some cases, a communication network may be comprised of multiple networks, even multiple heterogeneous networks, such as one or more border networks, voice networks, broadband networks, service provider networks, Internet Service Provider (ISP) networks, and/or Public Switched Telephone Networks (PSTNs), interconnected via gateways operable to facilitate communications between and among the various networks.
The phrase “communication protocol” generally refers to any type of communication protocol used to facilitate the exchange of information between two devices connected to a communication network. For example, a communication protocol may include any data transfer protocol request. In one embodiment, a communication protocol may be an application protocol including, but not limited to DNS, FTP, HTTP, IMAP, IRC, NNTP, POP3, SIP, SMTP, SNMP, SSH, TELNET, BitTorrent, and the like. In one embodiment, a communication protocol may be a transport protocol including, but not limited to DCCP, SCTP, TCP, RTP, UDP, IL, RUDP, and the like. Still yet in another embodiment, a communication protocol may be a network protocol including, but not limited to IPv4, IPv6, and the like. In accordance with one embodiment, a communication protocol may include an Ethernet protocol including, but not limited to Wi-Fi, Token ring, MPLS, PPP, and the like. Importantly, this definition is meant to be exemplary rather than limiting. As such, other protocols known to those skilled in the art are within the scope of this definition.
The terms “connected” or “coupled” and related terms are used in an operational sense and are not necessarily limited to a direct physical connection or coupling. Thus, for example, two devices may be couple directly, or via one or more intermediary media or devices. As another example, devices may be coupled in such a way that information can be passed there between, while not sharing any physical connection one with another. Based on the disclosure provided herein, one of ordinary skill in the art will appreciate a variety of ways in which connection or coupling exists in accordance with the aforementioned definition.
The phrases “in one embodiment,” “according to one embodiment,” and the like generally mean the particular feature, structure, or characteristic following the phrase is included in at least one embodiment of the present invention, and may be included in more than one embodiment of the present invention. Importantly, such phases do not necessarily refer to the same embodiment.
If the specification states a component or feature “may”, “can”, “could”, or “might” be included or have a characteristic, that particular component or feature is not required to be included or have the characteristic.
The term “responsive” includes completely or partially responsive.
FIG. 1 illustrates a block diagram showing the connection between a client and the Internet in accordance with one or more embodiments of the present invention. However, the choice of the Internet is for illustrative purposes and embodiments of the present invention are applicable to any type of communication network.
As shown in FIG. 1 , a client 10 , which according to one embodiment, may be a single computer or a computer network consisting of one or more computers. In the embodiment depicted, the computer(s) may be connected to the Internet 14 through an Internet Service Provider (ISP) 12 . The ISP 12 is typically a cable or telephone company that provides the infrastructure for the Internet 14 . This infrastructure consists of various elements of computer hardware and software, including physical cable connections, routers for connecting multiple connections, and computers for directing traffic, identifying users and authorizing access to the system.
According to one embodiment, communication between the client 10 and the Internet 14 uses TCP/IP (“transfer control protocol over internet protocol”). While a variety of different protocols are contained within TCP/IP, the most commonly used for retrieving webpages is the Hypertext Transfer Protocol (HTTP).
As such, when the client 10 wishes to access the Internet 14 using HTTP, the process shown in FIG. 2 is followed. Specifically, FIG. 2 illustrates a flowchart describing a process of interpreting a client HTTP request in accordance with one or more embodiments of the present invention. A request is sent ( 20 ) to retrieve a desired webpage. The request is interpreted ( 22 ) and the webpage is retrieved ( 24 ) and sent to the client ( 26 ), where the webpage code is run on the client computer to produce the webpage ( 28 ).
It is at this last step 28 where conventional methods of advertising over the Internet take place. Code for the desired advertisement may be placed within the webpage code and run at the same time the code for the webpage is run. Alternatively, the code for the desired advertisement may be placed as a separate webpage code. The resulting advertisement is then produced according to the extra code.
Typical advertisement code may include scripts that retrieve advertisements from other web servers (i.e. separate from the server which hosts the webpage code), that open new windows on the client computer to display advertisements, or that even temporarily display an advertising webpage prior to allowing the client to view the desired webpage.
Regardless of the method of advertising used, each method is initiated within the code for the webpage. In other words, it is the client's selection of webpage and running of the code for that webpage that determines both whether advertising will be displayed and the types of advertisements shown.
According to various embodiments of the present invention, additional computer software and/or hardware may provided by the ISP 12 (as seen in FIG. 1 ), enterprise, or by the end user. As a result, advertising content can be selected and delivered at the interpreting step 22 (see FIG. 2 ) as opposed to the code running step 28 (also in FIG. 2 ). Alternatively, advertising content may be selected and delivered based on the HTTP response at step 26 (see FIG. 2 ).
According one embodiment of the present invention, the content delivery system may include three components provided by the ISP 12 as shown in FIG. 3 . Content server 30 may be configured to store the content, such as advertisements, advertising content or other informational content, that is to be delivered to the client 10 . Insertion server 32 may be configured to monitor client traffic and act to detect a client's communication protocol request, e.g., a HTTP request, and/or a destination's communication protocol response, e.g., a HTTP response, and substitute content from the content server 30 for the requested content or supplement the requested content with content from the content server 30 . Alternatively, upon determining the existence of an active communication protocol connection or session between a destination and a client, the insertion server 32 may deliver content via another communication method by sending a message to the client's instant messenger, for example, while the HTTP session continues without interference.
In one embodiment, the insertion server 32 is implemented as a proxy server, transparent or not. The insertion server 32 may intercept all connections and connection with the destination on behalf of the client for all connections, whether needed to insert content or not. Alternatively, the insertion server 32 may only intercept connections when content insertion is desired as determined by the policy server 34 .
Policy server 34 may be configured to determine when insertion server 32 detects a request or response, what content is delivered from content server 30 , and how long the content is displayed to the client 10 , e.g., the duration until the client's original HTTP request is fulfilled.
While in the embodiment depicted, insertion server 32 is shown connected to the ISP 12 , for example, as part of a firewall between the client 10 and the Internet 14 , it may also be located between the client 10 and the ISP 12 . In this arrangement, rather than content hosted and provided by the ISP 12 at its level of the Internet infrastructure, the content may hosted at the network level of the client 10 . For example, a location that provides Internet access to multiple clients, such as an enterprise, library or an Internet cafe, may set up its own content delivery system at its network connection to the ISP 12 in order to transmit selected content to clients on its network. In this configuration, the system may be set up as part of a network firewall to minimize overhead.
FIG. 4 and FIG. 5 . illustrate how the TCP/IP process may be modified in accordance with various embodiments of the present invention. Specifically, FIG. 4 illustrates a flowchart representative of a process of detecting and intercepting a client TCP/IP request in accordance with one or more embodiments of the present invention. Those skilled in the art will appreciate similar modifications may be made to the TCP/IP process when detecting and/or intercepting TCP/IP responses destined for a client.
FIG. 4 , illustrates a “pass-through” method whereby the HTTP request is intercepted before reaching its intended destination. According to this embodiment, when the system is active, it waits for a client TCP/IP request to be detected 40 . If there is no request, the system waits for one to be detected 60 . This detection step 40 may be incorporated as part of existing firewall monitoring processes, such as the process used by a firewall to monitor for viruses and unauthorized network access attempts, for example.
Once a TCP/IP request is detected 40 , it is intercepted 41 and the desired content is selected 42 , retrieved 44 from the content server and sent 46 to the client. In one embodiment, the content may be selected based on information contained within the communication protocol request and/or response, such as information indicative of the client (e.g., an IP address used alone or as an index or key to retrieve a profile associated with the client), information indicative of the destination (e.g., an IP address used alone or as an index or key to retrieve a profile associated with the destination), the Request-URI in the HTTP request method, the Host field in the HTTP request header, the content in the response, such as the webpage content (e.g., keywords in the page).
After the content is sent 46 , the process delays 48 thereby displaying the content to the client for a fixed amount of time before processing the original TCP/IP request 50 . In this embodiment, the insertion server 32 acts as a proxy server handling the original TCP/IP request.
Alternatively, content may be delivered via a different communication method than used to detect the client/destination connection, concurrently with or completely in lieu of the requested content via the same communication method used to detect the client/destination connection.
According to yet another alternative embodiment, the insertion server 32 may determine the need for and/or select appropriate content to be delivered to the client based upon a “pass-through” method involving intercepting of HTTP responses before they reach the client.
FIG. 5 illustrates a flowchart describing a process of detecting and inserting content into a TCP connection in accordance with one or more embodiments of the present invention. According to the embodiment shown in FIG. 5 , a “pass-by” methodology may be used. In this embodiment, network packets are examined 70 as they pass by on the network. When a TCP/IP request is detected 72 , it is checked 76 against the policy for content insertion to determine if the packet should be intercepted. If the TCP/IP request is not to be intercepted, no action is taken and the TCP/IP request proceeds to its intended destination 78 . If no TCP/IP request is detected, or the request is allowed to proceed the system resumes examining packets 74 .
According to one embodiment, if the TCP/IP request is to be intercepted, then two actions may be taken. First, a canceling message may be sent 80 to the destination to negate the TCP/IP request. Second, the desired substitute or supplemental content may be selected 42 , retrieved 44 and sent 46 to the client in lieu of or in addition to the content requested by the intercepted TCP/IP request.
According to one embodiment, the timing of the canceling message is such that it reaches the destination and the substitute or supplemental content is sent to the client before the destination can respond to the TCP/IP request. The system then delays 48 for a period of time to allow the substitute or supplemental content to be displayed at the client before resuming 74 the packet examination process.
In one embodiment, the original TCP/IP request may need to be re-sent by the client after the delay period 48 for displaying the content. If the canceling message 80 fails to reach the destination before it responds to the original TCP/IP request, the response will be ignored by the client as long as the content is sent 46 to the client before the response from the destination as the TCP connection has effectively been hijacked.
According to one embodiment, policy server 34 may require a limited number of instructions to execute the desired method of content insertion. In one embodiment, the instructions may specify the timing of detecting and intercepting (if required) a client's TCP/IP request and the duration of sending the advertisement to that client and completing (if necessary) the TCP/IP request. For example, a list of instructions for the pass-through method might include:
1) Every hour, begin the detection process on the insertion server 32 ; 2) For the next two minutes, intercept each TCP/IP request and send advertising content in addition to or in lieu of the content requested by the TCP/IP request; 3) For each intercepted TCP/IP request, complete that request ten seconds after sending the advertising content.
The last step of completing the original TCP/IP request is preferable, but optional according to various embodiments. Alternatively, according to one embodiment, the client may be required to re-send the TCP/IP request in the same manner that existing webpage-based interrupt advertising works. In accordance with one embodiment, during the advertising delay, the client cannot re-send the TCP/IP request until the time specified for the delay (ten seconds in the above example) has expired. This latter method may be preferable for certain types of non-advertising content which are discussed below.
According to various embodiments, more complex selection algorithms may be used. According to one embodiment, a selection algorithm may include identifying clients for advertising, thus allowing for more targeted advertising to clients and selective delivery of advertising content. This algorithm may also use certain content in the HTTP request (e.g. the domain or IP information) to select content suitable for the client.
Also, according to one embodiment, multiple insertion servers 32 can be used. When multiple insertion servers 32 are provided, a reduction on the load on each individual server may result as well as the ability to differentiate clients based on the server. According to one embodiment, this system may create different advertising system potentials for the ISP. For example, a system with multiple insertion servers 32 may (i) allow clients who pay a premium to have reduced or no advertising content, (ii) facilitate setting different advertising rates for regions which use more or less bandwidth, and/or (iii) allow individual servers to be provided for ISP clients which have their own large internal computer networks (large companies, universities, etc.).
While the above embodiments describe the use of advertising content, it is contemplated that the systems and methods described here in may be easily adapted for use with other types of suitable content. For example, a corporation may use the system to provide employees with daily updates and other information, with the assurance that the information is more likely to be read than if the information were transmitted via email alone. According to one embodiment, the systems and methods may be used by governments to provide emergency and disaster information, much in the same way that the Emergency Broadcasting System is used on television and radio.
Accordingly, while this invention has been described with reference to illustrative embodiments, such as the Internet and HTTP, this description is not intended to be construed in a limiting sense. Importantly, applications of various embodiments of the present invention are applicable to a wide variety of communication networks and communication protocols. Various modifications of the illustrative embodiments, as well as other embodiments of the invention, will be apparent to persons skilled in the art upon reference to this description.
Exemplary Computer System Overview
Embodiments of the present invention include various steps, which will be described in more detail below. A variety of these steps may be performed by hardware components or may be embodied in machine-executable instructions, which may be used to cause a general-purpose or special-purpose processor programmed with the instructions to perform the steps. Alternatively, the steps may be performed by a combination of hardware, software, and/or firmware. As such, FIG. 6 is an example of a computer system 60 , such as a client or server (e.g., web server, content server, insertion server or policy server) with which embodiments of the present invention may be utilized. According to the present example, the computer system includes a bus 61 , at least one processor 62 , at least one communication port 63 , a main memory 64 , a removable storage media 65 a read only memory 66 , and a mass storage 67 .
Processor(s) 62 can be any know processor, such as, but not limited to, an Intel® Itanium® or Itanium 2® processor(s), or AMD® Opteron® or Athlon MP® processor(s), or Motorola® lines of processors. Communication port(s) 63 can be any of an RS-232 port for use with a modem based dialup connection, a 10/100 Ethernet port, or a Gigabit port using copper or fiber. Communication port(s) 63 may be chosen depending on a network such a Local Area Network (LAN), Wide Area Network (WAN), or any network to which the computer system 60 connects.
Main memory 64 can be Random Access Memory (RAM), or any other dynamic storage device(s) commonly known in the art. Read only memory 66 can be any static storage device(s) such as Programmable Read Only Memory (PROM) chips for storing static information such as instructions for processor 62 .
Mass storage 67 can be used to store information and instructions. For example, hard disks such as the Adaptec® family of SCSI drives, an optical disc, an array of disks such as RAID, such as the Adaptec family of RAID drives, or any other mass storage devices may be used.
Bus 61 communicatively couples processor(s) 62 with the other memory, storage and communication blocks. Bus 61 can be a PCI/PCI-X or SCSI based system bus depending on the storage devices used.
Removable storage media 65 can be any kind of external hard-drives, floppy drives, IOMEGA® Zip Drives, Compact Disc-Read Only Memory (CD-ROM), Compact Disc-Re-Writable (CD-RW), Digital Video Disk-Read Only Memory (DVD-ROM).
Optionally, operator and administrative interfaces (not shown), such as a display, keyboard, and a cursor control device, may also be coupled to bus 61 to support direct operator interaction with computer system 60 . Other operator and administrative interfaces can be provided through network connections connected through communication ports 63 .
The components described above are meant to exemplify some types of possibilities. In no way should the aforementioned examples limit the scope of the invention, as they are only exemplary embodiments.
In conclusion, the present invention provides novel systems, methods and arrangements for delivering advertising content to client systems. While detailed descriptions of one or more embodiments of the invention have been given above, various alternatives, modifications, and equivalents will be apparent to those skilled in the art without varying from the spirit of the invention. Therefore, the above description should not be taken as limiting the scope of the invention, which is defined by the appended claims. | Systems and methods for transmitting content to a client via a communication network are provided. According to one embodiment, a system includes a content server, an insertion server and a policy server. The content server stores and selects substitute or supplemental content. The insertion server monitors client traffic, detects client TCP/IP requests or destination TCP/IP responses and sends the selected substitute or supplemental content retrieved from the content server to the client in lieu of or in addition to content requested by the client TCP/IP requests or provided by the destination TCP/IP responses. The policy server provides instructions to the insertion server with respect to timing of detecting the client TCP/IP requests or destination TCP/IP responses and a delay associated with completing the client TCP/IP requests or destination TCP/IP responses. The system operates independently of respective destinations of the client TCP/IP requests and respective sources of the destination TCP/IP responses. | 7 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. patent application Ser. No. 11/869,087, filed Oct. 9, 2007 and claims priority from U.S. Provisional Patent Application Ser. No. 60/886,819 filed Jan. 26, 2007.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] This invention relates to controlling the corrosion of metals. More particularly, this invention relates to compositions and methods for inhibiting corrosion of ferrous and non-ferrous metals, including alloys, in aqueous environments.
[0004] 2. Background Art
[0005] It is widely known that both ferrous and non-ferrous metals, including alloys, are subject to corrosion under certain circumstances. Corrosion is generally defined as any deterioration of essential properties in a material due to chemical interaction with its environment, and in most situations it is considered to be undesirable. On a molecular level, corrosion is the consequence of the loss of an electron of a metal as it reacts with, in many cases, water and oxygen, and/or other oxygenating agents. The result of these interactions is usually formation of an oxide and/or a salt of the original metal. In most cases corrosion comprises the dissolution of a material. It may also be caused by exposure to corrosive chemicals, including, for example, acids, bases, dehydrating agents, halogens and halogen salts, organic halides and organic acid halides, acid anhydrides, and some organic materials such as phenol.
[0006] In order to combat corrosion, it is well known to treat, contact, or surround any susceptible metal, i.e., any having a thermodynamic profile that is relatively favorable to corrosion, with a so-called corrosion inhibitor. Because the efficacy of any particular corrosion inhibitor is generally known to be dependent upon the circumstances under which it is used, a wide variety of corrosion inhibitors have been developed and targeted for use. One target of great economic interest is the treatment of crude oils and gas systems, for protecting the variety of ferrous and non-ferrous metals needed for obtaining and processing the oils and gases. Such metals are present in oil and gas wells, including, for example, production and gathering pipelines, where the metals may be exposed to a variety of acids, acid gases such as CO 2 and H 2 S, bases, and brines of various salinities. Other applications include industrial water treatments, construction materials, coatings, and the like. In some cases the corrosion inhibitors are desirably tailored for inhibiting specific types of corrosion, and/or for use under particular conditions of temperature, pressure, shear, and the like, and/or for inhibiting corrosion on a generalized or localized basis.
[0007] A number of corrosion inhibitors featuring sulfur containing compounds have been described. For example, U.S. Pat. No. 5,863,415 discloses that thiophosphorus compounds of a specific formula are particularly useful for corrosion inhibition in hot liquid hydrocarbons and may be used at concentrations that add to the fluid less of the catalyst-impairing phosphorus than some other phosphorus-based corrosion inhibitors. These thiophosphorus compounds also offer the advantage of being able to be prepared from relatively low cost starting materials.
[0008] Other sulfur-containing compounds are disclosed in, for example, U.S. Pat. No. 5,779,938, which describes corrosion inhibitors that are reaction products of one or more tertiary amines and certain carboxylic acids, preferably a mixture of mercaptocarboxylic and carboxylic acids. The use of sulfhydryl acid and imidazoline salts are disclosed as inhibitors of carbon corrosion of iron and ferrous metals in WO 98/41673. Corrosion of iron is also addressed in WO 99/39025, which describes using allegedly synergistic compositions of polymethylene-polyaminodipropion-amides associated with mercaptoacids. A number of specifically sulfur-containing compounds are currently in commercial use as corrosion inhibitors for certain types of systems.
[0009] In view of the above, it would be desirable in the art to identify additional methods and compositions for inhibiting or controlling corrosion of both ferrous and non-ferrous metals and that, in particular, may be useful in treating hydrocarbon-containing aqueous systems. As used herein, ferrous metals include, in some non-limiting embodiments, iron and steel.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 is a plot comparing corrosion rate performance of an inventive corrosion inhibitor and a conventional corrosion inhibitor at comparable concentrations.
SUMMARY OF THE INVENTION
[0011] In one aspect the present invention provides a method of inhibiting corrosion of metals, comprising contacting a metal in an aqueous environment wherein the metal is corrodible and a corrosion inhibitor composition comprising at least one compound selected from the group consisting of compounds adhering to one of the general formulas:
[0000]
[0000] wherein x is carbon, oxygen, nitrogen, or sulfur; R 1 , R 2 , R 3 , and R 4 are independently hydrogen or methyl, m and n are independently integers from 1 to 5, and p and q are independently integers from 1 to 4;
[0000]
[0000] wherein m is an integer from 3 to 4; and
[0000]
[0000] wherein m is an integer from 1 to 4 and n=4−m.
[0012] In another aspect the invention provides a method of inhibiting corrosion of metals, comprising contacting a metal in a water-containing hydrocarbon or gas stream wherein the metal is corrodible and an effective amount of a corrosion inhibitor composition comprising at least one compound selected from the group consisting of compounds adhering to one of the preceding Formulas.
[0013] In still another aspect the invention provides a composition for inhibiting corrosion of metals in an environment wherein the metal is corrodible, comprising a compound selected from the group consisting of compounds adhering to one of the preceding Formulas.
DETAILED DESCRIPTION OF THE INVENTION
[0014] The novel mercaptan-based corrosion inhibitors identified in the present invention have been found to be efficacious in inhibiting corrosion of both ferrous and non-ferrous metals, including elemental metals, metals under conditions where passivation is inhibited, such as mild steel, stainless steel, copper and other alloys; alloys such as brasses; mixtures thereof; and the like. These mercaptan-based corrosion inhibiting compositions may be used alone, in mixtures of one or more of those defined hereinbelow, or in mixtures including other known corrosion inhibitors. They are conveniently termed “mercaptan-based”, alternatively referred to as thiols, because each category includes organosulfur molecules having at least one —SH group (a “thiol” or “sulfhydryl” group), though in many embodiments these compounds contain a plurality of —SH groups.
[0015] The first group of novel mercaptan-based corrosion inhibiting compositions is defined as compounds adhering to the general formula
[0000]
[0000] wherein x is carbon, oxygen, nitrogen, or sulfur; R 1 , R 2 , R 3 , and R 4 are independently hydrogen or methyl; m and n are independently integers from 1 to 5; and p and q are independently integers from 1 to 4. Specific but non-limiting examples of this group include bis-2(-mercapto-1-methylpropyl) sulfide, 2-mercaptoethyl sulfide, 2-mercaptoethyl ether, 1,5-pentane dithiol, and the like.
[0016] The second group of compositions is defined as compounds adhering to the general formula
[0000]
[0000] wherein m is an integer from 3 to 4. Specific but non-limiting examples of this group include bis-(2-mercaptocyclopentyl) sulfide, bis-2(2-mercaptocyclohexyl) sulfide, and the like.
[0017] The third group of compounds adheres to the general formula
[0000]
[0000] wherein m is an integer from 1 to 4 and n=4−m. Specific but non-limiting examples of this group include tetrakis-(4-mercapto-2-thiabutyl)methane and the like.
[0018] The above groups of compounds may be prepared by any means and methods known to those skilled in the mercaptan preparation art, including but not limiting to selection of sulfur-containing starting materials and sulfonation of non-sulfur-containing starting materials. Examples of non-limiting methods include those described in Buter, J. and Kellogg, R. M., “Synthesis of Sulfur-Containing Macrocycles Using Cesium Thiolates,” J. Org. Chem., 1981, 46, 4481-4485, Ochrymowycz, L. A., Mak, C-P., Michna, J. D., “Synthesis of Macrocyclic Polythiaethers,” J. Org. Chem ., Vol. 39, No. 14, 1974, 2079-2084; and Gerber, D., Chongsawangvirod, P., Leung, A., Ochrymowycz, L. A., “Monocyclic Polythiaether 1,4,7-Trithiacyclononane,” J. Org. Chem., 1977, 42, 2644-2645; all of which are incorporated herein by reference in their entireties.
[0019] The corrosion inhibiting groups, and species thereof, defined hereinabove may be used for the purpose of inhibiting corrosion in any ferrous or non-ferrous metals, in both elemental and alloyed form. In certain non-limiting embodiments, examples of these metals include, but are not limited to, commonly used structure metals such as aluminum; transition metals such as iron, zinc, nickel, and copper; and combinations of these. In one non-limiting embodiment the selected material for which corrosion inhibition is desired is an alloy, such as a copper alloy or steel.
[0020] The corrosion inhibiting composition may be incorporated into the environment to which the corrodible material will be, or is being, exposed. Such environment, which includes some proportion of water, may be, in certain non-limiting embodiments, a brine, a hydrocarbon producing system such as a crude oil or a fraction thereof, or a wet hydrocarbon containing gas, such as may be obtained from an oil and/or gas well. It may be used in any proportion sufficient to accomplish the desired degree of corrosion inhibition. Such may vary from a part per billion (ppb) level to a percentage. For example, in some embodiments the corrosion inhibiting composition may vary from 100 ppb to 10,000 parts per million (ppm) in a water-containing liquid or gas hydrocarbon stream. In other embodiments the corrosion inhibiting composition may be used in an amount of from about 1 ppb to about 1 percent by volume in such hydrocarbon stream. Those skilled in the art will be able to carry out the routine experimentation needed to determine the effective level for a given corrodible material in a given environment.
[0021] The corrosion inhibiting compositions described herein may be, prior to incorporation into or with a given corrosive environment, in gas, liquid or solid form. If a solid form is used, such is desirably comminuted to a degree adequate to enable desirably controlled dissolution and/or dispersal in the corrosive environment. While particle size is not critical in the present invention, it has been found convenient to employ a corrosion inhibiting composition having particles whose diameter, in non-limiting embodiments, is from about 0.2 mm to about 1.5 mm, for employment in a corrosive environment at approximately ambient temperature. Higher temperatures will generally allow for equivalent rates of dissolution or dispersal of larger particles, while lower temperatures may necessitate smaller particles.
[0022] Incorporation of the novel corrosion inhibiting compositions of the invention may be by any means known to be effective by those skilled in the art. Simple dumping, such as into a drilling mud pit; addition via tubing in a suitable carrier fluid, such as water or an organic solvent; injection; or any other convenient means may be adaptable to these compositions. Large scale environments such as those that may be encountered in oil production, combined with a relatively turbulent environment, may not require additional measures, after or during, to ensure complete dissolution or dispersal of the corrosion inhibiting composition. In contrast, smaller, less turbulent environments, such as relatively stagnant settling tanks, may benefit from mechanical agitation of some type to optimize the performance of the corrosion inhibiting composition. Those skilled in the art will be readily able to determine appropriate means and methods in this respect.
[0023] Performance of a given corrosion inhibiting composition may be tested using any of a variety of methods, such as those specified by the American Society for Testing Materials (ASTM). One effective method, that tests the performance of a composition under conditions of moderate shear, involves a rotating coupon electrochemical technique described in ASTM: Standard Guide for Evaluating and Qualifying Oilfield and Refinery Corrosion Inhibitors in the Laboratory (Designation G170-01a), and also in NACE Publication 5A195, Item No. 24187, “State of the Art Report on Controlled-Flow Laboratory Corrosion Tests.” In this test, various concentrations of inhibitor chemistries are introduced into a given prospective, corrosive environment. The coupons are then rotated at high speed in the environment to generate moderate stress of their surfaces. Electrochemical techniques, such as, for example, linear polarization resistance, are then employed under these moderate shear conditions, to monitor the prevailing general corrosion rate as well as to identify instances of localized corrosion. A concentration profile is then generated in order to establish the minimum effective concentration of the corrosion inhibiting composition that is required to adequately protect the coupon at an acceptable corrosion rate.
[0024] The description hereinabove is intended to be general and is not intended to be inclusive of all possible embodiments of the invention. Similarly, the examples hereinbelow are provided to be illustrative only and are not intended to define or limit the invention in any way. Those skilled in the art will be fully aware that other embodiments within the scope of the claims will be apparent, from consideration of the specification and/or practice of the invention as disclosed herein. Such other embodiments may include selections of specific mercaptan-based compounds falling within the defined groups, and combinations of such compounds; proportions of such compounds; mixing and usage conditions, vessels, and protocols; hydrocarbon fluids and other fluids in which the corrosion inhibitor compositions may be used; performance in inhibiting or controlling corrosion; and the like; and those skilled in the art will recognize that such may be varied within the scope of the appended claims hereto.
EXAMPLES
Comparative Example 1
[0025] Two mercaptan-based compounds are compared via testing done using the procedure described in ASTM: Standard Guide for Evaluating and Qualifying Oilfield and Refinery Corrosion Inhibitors in the Laboratory (Designation G170-01a), and also in NACE Publication 5A195, Item No. 24187, “State of the Art Report on Controlled-Flow Laboratory Corrosion Tests.” One inhibitor composition contains 2-mercaptoethyl sulfide, which conforms to one embodiment of Formula 1 provided hereinabove. The other composition features an amide/imidazoline-based corrosion inhibitor and is used herein for comparative purposes.
[0026] The method includes use of a rotating cylinder electrode (RCE), a standard RCE coupon, and tube/cylinder C1018 supplied by Metal Samples, Inc. of Alabama. The corrosive environment is a combination of brine and a paraffinic hydrocarbon in an approximate weight proportion of 80:20, respectively.
[0027] During the test the coupons are rotated at approximately 6,000 revolutions per minute (rpm), and a temperature of approximately 160° F. is maintained in the corrosive environment. The test is carried out over a 17-hour time period.
[0028] The corrosion rate of the coupons is monitored electrochemically, by means of a linear polarization resistance (LPR) apparatus. To ensure that the comparison is fair, the amount of active inhibitor on a parts per million (ppm) basis in each of the inhibitor compositions is approximately the same.
[0029] The coupons are examined, post-testing, for localized corrosion using an optical microscope. Corrosion is measured as mils per year (mpy).
[0030] The results of the test are shown in FIG. 1 . The data plotted in FIG. 1 is also shown in tabular form in Table 1, comparing concentration of the inhibitor compound (“actives”) on a ppm basis with the level of corrosion measured post-test for each of the inhibitors.
[0000]
TABLE 1
Concentration of actives (ppm)
0.050
0.100
0.2
0.25
0.5
1
2
5
10
Amide/imidazoline-
154.8*
125.3*
103.4*
—
71.3*
35.2*
1.8*
0.2*
0.2*
based inhibitor*
(Corrosion rate, mpy)
2-mercaptoethyl sulfide
23.4
2.0
—
0.4
0.4
—
—
0.2
—
(Corrosion rate, mpy)
*indicates comparative only; not an example of the invention.
— indicates no data available. | Corrosion of both ferrous and non-ferrous metals, induced by a variety of corrosive aqueous-based environments, may be inhibited or controlled through use of corrosion inhibiting compositions comprising at least one member of certain formula-specified categories of mercaptan-based compounds. Where the compounds are appropriately selected, and particularly at low inhibitor concentrations, the compositions may inhibit corrosion to a degree that is comparable to or significantly greater than the inhibition provided by an equal amount of certain other corrosion inhibitor compounds. It is emphasized that this abstract is provided to comply with the rules requiring an abstract which will allow a searcher or other reader to quickly ascertain the subject matter of the technical disclosure. It is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims. | 2 |
FIELD OF THE INVENTION
The invention relates generally to system having two-way communication between devices. More specifically, the invention relates to external transceivers which remotely communicate with implanted medical devices. Part of this two-way communication link consists of control or programming signals transmitted from the external device to the implanted device for the purpose of altering the operation of the implanted device. The remainder of the link consists of low-level telemetry transmissions from the implant to the external device for the purpose of conveying information such as current status, battery level, or patient data.
BACKGROUND OF THE INVENTION
Two-way communication with implanted medical devices imposes special problems which become even more acute in an interference-prone environment, especially where the medical devices are essential to maintaining life functions. Necessarily, implanted medical devices require ultra-low power levels from long-lived batteries. The most common implanted telemetry system employs a single, multi-turned coil to externally receive the low-level telemetry signals. These single-coil, receiving antennas are quite susceptible to interference from electric, magnetic and electromagnetic field sources which are present in the clinical environment.
The present invention employs two noise-canceling, antenna coils, which improve the signal-to-noise ratio significantly, and a circuit which permits transmission and reception of signals through the same antenna coil network without interactive tuning problems and without the employment of any switching devices. The improved, external transceiver circuit permits two-way communications with implanted medical devices in close proximity (on the order of 4 inches to 2 feet) to common interference sources such as cathode ray tubes and video monitors. Moreover, because the antenna coils reside within the same plane and our preferably co-axial they require a minimum amount of volume, leading to a much smaller, more portable programmer head. Finally, a system featuring the present invention may be cheaper, due to the fact that the disclosed antenna may be constructed using printed circuit board, and thus be integrated with circuitry.
SUMMARY OF THE INVENTION
A medical system having improved telemetry, the medical system featuring a programmer having a programming head. The system provides improved telemetry due to the unique antenna scheme within the programmer head. The antenna scheme utilizes a first antenna and a second antenna, the antennas disposed in a concentric and co-planar manner. This concentric and co-planar disposition permits the programmer head to be of much smaller and, thus, a more portable size than was previously possible. The antenna is further coupled with circuitry or software or both to reduce far field response (noise). The antenna may be constructed using printed circuit board, and thus be integrated with circuitry.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A depicts the general configuration of a programmer in which the present invention may be used.
FIG. 1B is a detailed view of programmer head 14 .
FIG. 1C shows a block diagram of a system incorporating the telemetry receiver of this invention.
FIG. 1D is a detailed view of programmer head 14 and in particular illustrates the transmitting and receiving components 20 found within the head and the particular subject of the present invention.
FIG. 2 depicts the relation between the antenna coils 1 and 2 which would be within programming head 14 according to the present invention as they would relate to the transmitting antenna 3 from an implanted device.
FIGS. 3A-3C each disclose compensatory electrical controls which may be used to provide the desired far field cancellation result.
FIG. 4A shows the response of a single loop receiving antenna as a function of the distance to a transmitter and FIG. 4B shows the response of a dual loop receiving antenna as a function of the distance to a transmitter.
FIG. 5 shows an alternative embodiment of the present invention.
FIGS. 6A and 6B show an alternative means for providing far field noise-canceling effects.
FIG. 7 depicts an alternative embodiment for providing coils according to the present invention.
The FIGS. are not necessarily to scale.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1A depicts the general configuration of a programmer in which the present invention may be used. Typical programmer currently used, such as the Medtronic™ model 9790 programmer feature a keyboard 10 and display 12 . A series of one or more leads 16 are provided to provide direct electrical coupling to the patient, e.g. to collect ECG signals. Finally, a programmer head 14 is provided. This head transmits and receives signal through which the programmer may communicate with an implanted device 30 . In the present system head 14 transmits and receives RF signals.
FIG. 1B is a detailed view of programmer head 14 . As seen head 14 possesses a pair of push button switches 23 and 25 labeled INTERROGATE and PROGRAM respectively. In use, the physician depresses one or the other of the two buttons to initiate a series of communications with an implanted device. Also commonly provided on programming heads 14 is a light 22 to indicate the position of the head relative to the implanted device. That is the light may illuminate or change color depending upon the proximity of the head to an implanted device.
Referring now to FIG. 1C, there is shown a block diagram of a system incorporating the telemetry receiver of this invention. While the invention is described in the context of an external device which receives telemetry signals from an implanted medical device, the invention is not limited to the environment of medical devices.
An external device, such as a programmer used in cardiac pacing systems, is illustrated at 20 . The device picks up data at t/r coil 21 , which data has been telemetered from another device illustrated at 30 , e.g., an implanted cardiac pacemaker. The data which is uplinked to device 20 is inputted to processor block 24 via receiver 89 , where it may be stored, analyzed, etc. The data can be displayed by any suitable display or printer, as shown at 15 . Such programmer devices also have input capability, as by receiving tapes, discs, or data inputted by keyboard, as shown at 16 . Device 30 also has a transmitter 22 for sending data to the implanted device 30 . The portions of implanted device 30 that are important to this invention are illustrated within block 30 . The transmitter 31 is controlled by block 25 , and transmits encoded data through t/r coil 28 to the external device 20 . In practice, the device 30 can also receive data from external device 20 , through receiver 29 which is connected to processor 25 . Processor 25 is also suitably used to control operation of pace sense circuits 17 , which transmit pacing signals to a patient's heart through leads 18 , and receive heart signals for processing. Block 25 suitably uses a microprocessor and associated memory 26 , in a know fashion.
FIG. 1D is a detailed view of programmer head 14 and in particular illustrates the transmitting and receiving components 20 found within the head and the particular subject of the present invention. As mentioned above, programmers communicate with implanted devices through the transmission and reception of telemetry. Often this telemetry is carried on RF waves, which require the provision of appropriately configured antennas in the programming head 14 .
FIG. 2 depicts the relation between the antenna coils 1 and 2 which would be within programming head 14 according to the present invention as they would relate to the transmitting antenna 3 from an implanted device. As seen, the transmitting antenna 3 creates a field depicted here with a variety of flux lines, generally 4 . The coils 1 and 2 are in the same plane but do not have the same size. Moreover, these coils need not even have the same number of windings. Although shown as roughly square, coils may be in any appropriate shape, as discussed below more fully with regards to FIG. 9 . As shown, coils 1 and 2 are coupled to compensatory electrical controls to provide the far field noise canceling effect. As can be appreciated, the different sizes of coils 1 and 2 result in a different pick up of the magnetic flux of the field and, thus, induces different voltages in each of the coils. These different voltages may be compensated for by the compensatory electrical controls to thus achieve far field noise canceling effect.
FIGS. 3A-3C each disclose compensatory electrical controls which may be used to provide the desired far field cancellation result. Generally speaking, the voltage generated by a coil is linearly related to the number of turns and the area of the coil (assuming, for simplicity, a far field source which gives uniform magnetic flux per unit area.) Thus the more turns in a coil, or the larger the coil, the more voltage created. From this, we have found that coils of non-equal area can be compensated for by varying the number of windings in each. FIG. 3A is particularly beneficial when the inner coil antenna L 1 is smaller than outer coil L 2 and inner coil L 1 has more turns or windings to as to generate the same voltage for far fields, but in opposite phase. For example, a typical set of coils would have the following characteristics: The outer coil L 2 would be circular and be six square inches in area and have 25 turns while the inner coil L 1 would be on quarter the area, or one and one-half (1.5) square inches and have 100 turns.
FIG. 3B shows an alternative embodiment for providing far field cancellation. In particular, this embodiment features the step-up transformer T 1 which may be used to compensate for the small area of coil 2 . This use of a step-up transformer is particularly believed useful if the voltage loss cannot be made up for by providing coil 2 with more turns. Recall, the voltage induced in the coils by the field is a function of both the coil geometry as well as the number of turns in the coils. Thus the compensatory electrical control scheme used in the invention depends both upon the size of the coils as well as the number of turns used in each coil. Other factors which affect the ultimate design of a programmer head include, among other things, the carrier frequency, transmission power.
FIG. 3C shows an alternative embodiment for providing the compensatory electrical controls. In particular, this embodiment approaches the desired far field noise canceling effect in a manner opposite to that shown in FIG. 3 B. In particular, in this design, rather than stepping up the output from coil L 2 the output from coil L 1 is attenuated.
FIG. 4A shows the response of a prior art single loop receiving antenna as a function of the distance to a transmitter and FIG. 4B shows the response of a dual loop receiving antenna according to the present invention as a function of the distance to a transmitter. As can be seen in a comparison of these FIGS, a dual coil, concentric co-planar antenna of the present invention provides superior performance compared to a single coil version. This is seen specifically in FIG. 4A, where a single coil has a gain of 30 versus FIG. 4B, where a dual coil antenna has a gain of 100, both being 0.00 meters distance (Z).
FIG. 5 shows an alternative embodiment of the present invention. In this embodiment a further third coil 97 is provided alongside and in the same plane as a co-planar and co-axial coil design 98 , 99 as previously described above. In addition, third coil 97 , besides being provided alongside and in the same plane as a co-planar and co-axial coil design 98 , 99 , could also be provided co-planar and co-axial to coil 98 , 99 instead of alongside. In this last configuration there would be a tri-coil array in a single plane and all of which would be concentric. The additional third coil may be used to accommodate rotated uplink fields. This additional coil will be switched in, instead of the inner coil, upon such occurrence. Through this structure there is a butterfly type receiving type structure. It should be pointed out, this design does have a disadvantage to the concentric design in that it has two optimal positions and it does have a null output depending upon the rotation along the Z axis. Despite these limitations the additional third co-planar coil provides greater freedom in trading of far field, close field responses. The range of such structure, however, will be limited, as the turn's ratios cannot be very large.
FIGS. 6A and 6B shows an alternative means for providing far field noise-canceling effects. In particular, FIG. 6A shows a structure in which two coils may have their signals processed within their digital domain. Coils L 1 , L 2 (coil 1 and coil 2 ) are disposed in a co-planar, co-axial manner, as already described above. As seen, each coil itself is coupled through an amplifier to an analog/digital converter. Thereafter the digital signals of each coil are processed using a digital signal processor, as shown.
FIG. 6B shows the steps used to process the signals gathered by the structure in FIG. 6 A. As seen, the signals are received or taken from coil 1 and coil 2 at 6 - 1 . Thereafter, at 6 - 2 signals outside the band of telemetry frequencies are removed and the ratio of non-zero filtered signals is performed at 6 - 3 . At 6 - 4 the result of the operation in 6 - 3 is processed along side the original sent signals from 6 - 1 so as to achieve the appropriate far field noise suppression, depicted here as processed signal at 6 - 5 .
FIG. 7 depicts an alternative embodiment for providing coils according to the present invention. While the invention disclosed above is preferably practiced using congruent coil shapes which are disposed co-axially, in a particular environment the invention may also be practiced using non-congruent or non co-axial or both coils. Examples of such coils are shown in FIGS. 7A-7E.
FIG. 7A depicts a scheme in which dual oval coils are set in a non co-axial disposition.
FIG. 7B shows co-axial disposition of a square outer coil and circular inner coil. In both FIGS. 7A and 7B the coils are set in a planar configuration.
In FIG. 7C the coils are set in a manner in which they have different or varying thicknesses. In this configuration they would be co-planar and, indeed, they could even be congruent, although not necessarily. While depicted as co-axial it could also be imagined they could be in a non co-axial configuration.
FIG. 7D depicts an alternative embodiment in which the coils are co-axial and planar but which have a ramped or increasing thickness within the plane.
Finally, FIG. 7E depicts an embodiment in which the coils are disposed in a co-planar, co-axial configuration but with the outer coil having a greater thickness than the inner coil. It should be understood, as discussed above, that the windings of each coil may be suitably selected to obtain the desired output signals for the environment in which the antenna is to operate. Thus, the present invention has been described within the context of a medical system programmer. It should be understood, however, the antenna of the present invention is not limited merely to medical systems but could congruently be used in other applications as well, such as in a variety of wireless devices. | A medical system having improved telemetry, the medical system featuring a programmer having a programming head. The system provides improved telemetry due to the unique antenna scheme within the programmer head. The antenna scheme utilizes a first antenna and a second antenna, the antennas disposed in a concentric and co-planar manner. This concentric and co-planar disposition permits the programmer head to be of much smaller and, thus, a more portable size than was previously possible. The antenna is further coupled with circuitry or software or both to reduce far field response (noise). The antenna may be constructed using printed circuit board, and thus be integrated with circuitry. | 7 |
More than one application for the Reissue of U.S. Pat. No. 6,592,908 has been filed. The reissue applications are the present application and U.S. Ser. No. 11/181,001, filed Jul. 13, 2005, and issued as U.S. Pat. RE 39,734 on Jul. 17, 2007.
STATEMENT OF PRIORITY
This application is a division of U.S. Ser. No. 11/181,001, filed Jul. 13, 2005 and which issued as U.S. Pat. RE 39,734 on Jul. 17, 2007, which is a reissue of U.S. Pat. No. 6,592,908 which issued on Jul. 13, 2005 from U.S. Ser. No. 10/252,957, filed Sep. 23, 2002, the disclosures of which are hereby incorporated by reference herein.
FIELD OF THE INVENTION
This invention relates to nutritional or therapeutic compositions useful for treating mammals to increase their body content of glutathione above a pretreatment level thereby to enhance the immune activity of the treated mammal. More specifically, it relates to compositions containing a selenium compound together with a glutathione precursor which is a mixture of glutamic acid, cystine and glycine.
BACKGROUND OF THE INVENTION
Glutathione is a tripeptide and a major reducing agent in the mammalian body. Its chemical structure is:
or, more simply
GLU-CYS-GLY
Its chemical name is glutamyl-cysteinyl-glycine.
Like many other small peptides in the mammalian body, it is not synthesized by procedures involving DNA, RNA and ribosomes. Rather, it is synthesized from the amino acids available in the body by procedures utilizing enzymes and other body components such as adenosine triphosphate as an energy source.
It is generally recognized that many disease processes are attributed to the presence of elevated levels of free radicals, reactive oxygen species (ROS) and reactive nitrogen species (RNS), such as superoxide, hydrogen peroxide, singlet oxygen, peroxynitrite, hydroxyl radicals, hypochlorous acid (and other hypohalous acids) and nitric oxide.
Mammalian cells have numerous mechanisms to eliminate these damaging free radicals and reactive species. One such mechanism includes the glutathione system, which plays a major role in direct destruction of reactive oxygen compounds and also plays a role in the body's defense against infection.
It is known that insufficient levels of glutathione may result in the onset of numerous diseases. Diseases of aging appear to be associated with a drop in glutathione levels. Moreover, since there is no evidence of transport of glutathione into cells, glutathione must be produced intra cellularly.
One of the most important contributions of glutathione to mammalian health is its participation in the proper functioning of the immune system to respond to infection or other types of trauma. It is known that weakening of the immune system caused by infection or other traumas occurs concurrently with depletion of glutathione in body tissues. It is known, also, that such weakening can be reversed by replenishing the supply of glutathione. It is believed that glutathione accomplishes its salutary effects by protecting immune cells against the ravages of oxidizing agents and free radicals.
There is a need for compositions and methods to aid in elimination of damaging free radicals and reactive oxygen and nitrogen species. One possible mechanism for achieving this may be through enhancement of glutathione levels in patients utilizing precursors for glutathione synthesis.
There is some question as to whether orally ingested glutathione is available to enhance the immune system. Since it is a tripeptide, conventional wisdom suggests that it would be hydrolyzed in the intestinal system to release the free amino acids. Even if some of the tripeptide gets through the gastrointestinal wall intact, it is questionable whether it can be absorbed as such into the individual cell, rather than being synthesized intracellularly. Some experts are of the opinion that glutathione resists hydrolysis when taken orally. In any event, it is generally acknowledged that an increase in tissue and cellular concentrations of glutathione facilitates resistance to infective agents by enhancing the immune system.
The mucous membrane is the membrane which lines those body passages which communicate directly or indirectly with the exterior. For purposes of this invention, the important parts of the mucous membrane are those portions which line the oral passage, the nose, the anus and the vagina since the compositions are intended for sublingual, buccal, nasal, anal and or vaginal delivery. Oral delivery by sublingual or buccal routes is much preferred because of its convenience. Such delivery may be, for example, in the form of pills, lozenges and tablets which may be retained in the mouth until dissolved. In rare instances, parenteral delivery may be utilized, but this is normally not necessary.
BRIEF SUMMARY OF THE INVENTION
The essential components of the compositions of this invention are:
1. A selenium precursor together with
2. Glutamic acid, cystine and glycine.
The separate components serve as precursors for the metabolic formation of glutathione after they have been transported across the mucous membrane.
The compositions may be used alone but, normally they will be employed in association with one or more non-toxic pharmaceutically acceptable carriers appropriate to the method of administration.
The compositions will be utilized to increase the formation of glutathione and thus to enhance the immune activity of a mammal in need of such treatment. The effect of the treatment is such that after the treatment, the mammal will be more resistant to microbial infection or other trauma adversely affecting immune activity than before such treatment.
Because of their ability to increase production of glutathione, the compositions are useful to treat a wide variety of diseases associated with the presence of excess free radical or reactive oxygen or nitrogen species. These include, for example, cancer, Alzheimer's disease, arteriosclerosis, rheumatoid arthritis and other autoimmune diseases, cachexia, coronary artery disease, chronic fatigue syndrome, AIDS and others as will be apparent to the skilled artisan.
DETAILED DESCRIPTION OF THE INVENTION
In accordance with the present invention, the compositions described and claimed herein will contain components suitable for the anabolic production of glutathione once they have been transported through the mucous membrane. As presently conceived, the precursors of glutathione are glutamic acid, cystine and glycine.
It will be appreciated by the skilled artisan that the proposed components are amphoteric and therefore may be employed as non-toxic metal salts or acid addition salts. Typically, the salts are alkalic or alkaline earth metal salts, preferably sodium, potassium or calcium salts. Suitable acid addition salts include salts of hydrochloric, phosphoric and citric acid.
The amino acids may also be employed in the form of certain of their derivatives including esters and anhydrides which before or after transport through the mucous membrane will be modified into the form in which they will be joined together to form glutathione.
All of this will be readily appreciated by those skilled in the art. Accordingly, when the terms glutamic acid, cystine, glycine are employed both in the specification and claims they will be understood to mean not only the products themselves, but also those derivatives which can be converted to a unit of the glutathione molecule.
The sulfur containing amino acid in the compositions of this invention is cystine. The sulfur containing amino acid moiety in glutathione is cysteine. The latter contains a sulfhydryl group. In the former molecule, two cysteine molecules are joined via a disulfide bond.
However, it is not possible to utilize cysteine in compositions for mammals because it is somewhat toxic. Accordingly, in the compositions of this invention, cystine is used. Upon reductive cleavage of the disulfide bridge, two molecules of cysteine are formed. Thus each molecule of cystine is capable of forming two molecules, of cysteine, each of which will join with glutamic acid and glycine to form two molecules of glutathione.
Of course all amino acids employed in this invention, except glycine which does not form optical isomers, are in the natural or L-form.
Although wide variations are possible, it will be apparent that the optimum ratio of glutamic acid to cystine to glycine in the novel compositions described herein is 1:0.5: 1. If an excess of any acid is used, it will presumably be of nutritional value or may simply be metabolized.
As will be apparent to the skilled artisan, the only component in the novel compositions of this invention which may be toxic is selenium. Accordingly, in providing dosage units for mammalian administration by any selected route, the limiting factor is to avoid treatment either with single or multiple dosage units at such levels that the total delivery of selenium is close to its toxic limit.
The recommended daily allowances for elemental selenium as reported in The Pharmacological Basis of Therapeutics, Ninth Edition, page 1540, The McGraw-Hill Companies, 1996 are as follows:
Years
ug
Infants
0.0-0.5
10
0.5-1.0
15
Children
1-3
20
4-6
20
7-10
30
Males
11-14
40
15-18
50
19-24
70
25-50
70
51+
70
Females
11-14
45
15-18
50
19-24
55
25-50
55
50+
55
Pregnant
—
65
Lactating
1 st six months
75
2 nd six months
75
The recommended daily dosage for humans therefore ranges from 10 to 75 μg per day. For animals the range may be generally higher but will, of course, depend upon the animal and its size.
The precise amount of the therapeutically useful compositions of this invention for daily delivery and the duration of the period of such delivery will depend upon the professional judgment of the physician or veterinarian in attendance. Numerous factors will be involved in that judgment such as age, body weight, physical condition of the patient or animal and the ailment or disorder being treated.
Selenium is one of numerous trace metals found in many foods. In the compositions of this invention, selenium may be employed as one of several non-toxic, water soluble organic or inorganic selenium compounds capable of being absorbed through the mucosal membrane. The presently preferred inorganic selenium compounds are aliphatic metal salts containing selenium in the form of selenite or selenate anions. However, organic selenium compounds are more preferred because they are normally less toxic than inorganic compounds. Other selenium compounds which may be mentioned by way of example include selenium cystine, selenium methionine, mono- and di-seleno carboxylic acids with about seven to eleven carbon atoms in the chain. Seleno Amino acid chelates are also useful. Any of these selenium compounds may be considered for use in the present invention as selenium precursors.
It is important for the practice of this invention that the selenium as employed in the composition be capable of transport through the mucosal membrane of the patient under treatment. For this reason, water insoluble selenium compounds are not generally useful.
For convenience, the term “selenium” is sometimes used hereinafter to include any of the various water soluble selenium products which can be transported through the mucosal membrane in the practice of this invention. It will be understood, however, that the particular forms of selenium compounds set forth herein are not to be considered limitative. Other selenium compounds, which exhibit the desired activity and are compatible with the other components in the mixture and are non-toxic, can be used in the practice of the invention. Many of them are available commercially.
In fact, the amount of selenium precursor employed in the novel compositions is only enough to provide a catalytic quantity of the element to activate the glutathione system. The catalytic quantity of selenium precursor utilized in the compositions of this invention is such that it will produce either in one dosage unit or in multiple dosage units sufficient elemental selenium to promote the production and activation of glutathione. Typically, this will be at or near the recommended daily allowance of selenium for the individual mammal under treatment. This amount will be well below the toxicity limit for elemental selenium. By way of non-limiting examples, a representative range of catalytic quantities of selenium precursors is set forth in the present application in paragraph [0026] on page 6, as shown to be effective based on the age of the individual.
As indicated above, the presently preferred method of transdermal delivery for the novel compositions is oral, either sublingual or buccal. It is convenient to provide dosage units for such delivery in the form of pills, lozenges or tablets such as gelled tablets which will slowly dissolve in the mouth.
Nasal delivery will typically be accomplished by sprays or drops. Suppositories will be useful for rectal or vaginal delivery.
This invention provides pharmaceutical compositions used in the method of the invention. Such compositions comprise a therapeutically effective amount of combined glutamic acid, cystine, glycine and a selenium precursor in a pharmaceutically acceptable carrier. In a particular embodiment, the term “pharmaceutically acceptable” means one that is generally recognized as safe, approved by a regulatory agency of the federal or a state government or listed in the U.S. Pharmacopeia or other generally recognized pharmacopeia for use in animals, and more particularly in humans. The term “carrier” refers to a diluent, adjuvant, excipient, or vehicle with which the active compounds are administered.
The compositions which may be provided in bulk or dosage unit form are prepared in accordance with standard pharmaceutical practice and may contain excipients such as starch, glucose, lactose, sucrose, gelatin, malt, rice, flour, chalk, silica gel, sodium stearate, glycerol monostearate, talc, sodium chloride, dried skim milk, glycerol, propylene, glycol, water, ethanol and the like. Sterile liquids, such as water and oils, including those of petroleum, animal, vegetable or synthetic origin, such as peanut oil, soybean oil, mineral oil, and sesame oil may also be useful. The composition, if desired, can also contain minor amounts of wetting or emulsifying agents, coloring agents or buffering agents.
Buffering agents are sometimes used in the compositions of the invention to maintain a relatively constant hydrogen ion concentration in the mouth (pH about 7.5) or other point of entry. An appropriate buffering agent may be selected from numerous known reagents including, for example phosphate, carbonate and bicarbonate systems. Alpha-lactalbumin is useful because of its buffering properties. Additionally, it is non-toxic, water soluble and contains appreciable amounts of the required amino acids.
The compositions may also contain mucous membrane penetration enhancers such as sodium lauryl sulphate, sodium dodecyl sulphate, cationic surfactants such as palmitoyl DL camitine chloride, cetylpyridinium chloride, non-ionic surfactants such as polysorbate 80, polyoxyethylene 9-lauryl either, glyceryl monolaurate, polyoxyalkylenes, polyoxyethylene 20 cetyl ether, lipids such as oleic acid, bile salts such as sodium glycocholate, sodium taurocholate and related compounds.
Examples of these suitable carriers are described in Remington's Pharmaceutical Sciences, Nineteenth Edition (1990), Mack Publishing Company, Easton, Pa. in Handbook of Pharmaceutical Excipients, published by The American Pharmaceutical Association and The Pharmaceutical Society of Great Britain (1986) and the Handbook of Water-Soluble Gums and Resins, ed. By R. L. Davidson, McGraw-Hill Book Co., New York, N.Y. (1980). Compositions and methods of manufacturing compositions capable of absorption through the mucosal tissues are taught in U.S. Pat. No. 5,288,497. These publications are incorporated by reference herein in their entirety. They can be readily employed by the skilled artisan to devise methods of delivery other than those specifically described in this disclosure.
The compositions of the invention are most conveniently utilized in dosage units for oral administration. They may be used alone but are preferably provided as tablets, suitably sublingual tablets. Such tablets may be prepared in one a day form or for intermittent use throughout the day, for example every three hours.
The tablets will typically weigh from about 0.5 to 5 grams and will contain a therapeutically effective amount of the essential ingredients together with the selected vehicle. “Therapeutically effective” as used herein means the amount of the composition which is sufficient to achieve the desired result, i.e., enhancement of the immune system. It means that the immune system is more effective in combating infection after treatment than it was before treatment.
A particular advantage of the compositions of the invention is that they can be provided in a number of different forms and at dosage levels appropriate to the individual mammal being treated. For example, tablets, elixers, solutions, emulsions, powders, capsules and other forms can be provided for one a day treatment or successive treatments on the same day for animals or humans whether male or female, whether infant, adolescent or adult. The defining feature of this advantage is the amount of selenium precursor utilized since the other components are essentially non-toxic.
Referring to the table above, tablets and other forms of the immunoenhancing compositions can be prepared to provide any quantity of elemental selenium from less than 1 μg to 7.5 μg. For example, a tablet containing 10 μg of selenium methionine is capable of delivering 4 μg of elemental selenium, and 7.5 μg of selenium methionine is capable of delivering 3 μg of selenium. Tablets may be given several times per day to achieve the desired immune enhancing effect.
A one a day tablet weighing two grams may contain 200 mg or more of the composition. A similar tablet intended to be used every four hours may contain 50 mg to 100 mg or more of the therapeutically effective composition. Equivalent amounts of carrier and active components will be utilized in other compositions designed for other methods of administration.
The following examples are given by way of illustration only and are not to be considered a limitation since many apparent variations are possible without departing from the spirit or scope of the invention.
EXAMPLE 1 (TABLET)
Ingredients:
89
mg
cystine
75
mg
glycine
147
mg
glutamic acid
22.5
μg
polyvinylpyrolidone
61.25
mg
lactose
4.5
ml
alcohol SD3A-200 proof
9
mg
stearic acid
42.3
mg
corn starch
10
μg
selenium methionine
Blend the cystine, glycine, glutamic acid, polyvinylpyrrolidone and lactose together and pass through a 40 mesh screen. Add the alcohol slowly and knead well. Screen the wet mesh through a 4 mesh screen. Dry the granulation at 50 degrees centigrade for 10 hours. Pass the mixture of stearic acid, corn starch and selenium compound through a 60 mesh screen and tumble with the granulation until all the ingredients are well mixed. Compress using a 7/16 inch standard concave punch.
EXAMPLE 2 (TABLET)
Ingredients:
178
mg
cystine
150
mg
glycine
294
mg
glutamic acid
5
μg
selenium methionine
126
mg
lactose
78
mg
potato starch
96
mg
ethyl cellulose
54
mg
stearic acid
Thoroughly mix the ingredients in a blender, dry, put through a 12 mesh screen and compress into tablet using a 13/32 inch concave punch. | Nutritional or therapeutic compositions containing glutamic acid, cystine, glycine and a selenium precursor and methods for their utilization to increase glutathione synthesis and thereby enhance the immune system are described. | 0 |
The invention herein described was made in the course of or under a contract or subcontract thereunder with the Department of Air Force.
BACKGROUND OF THE INVENTION
Process fluid or gas bearings are now being utilized in an increasing number of diverse applications. These fluid bearings generally comprise two relatively movable elements with a predetermined spacing therebetween filled with a fluid such as air, which, under dynamic conditions forms a supporting wedge sufficient to prevent contact between the two relatively movable elements.
More recently, improved fluid bearings, particularly gas bearings of the hydrodynamic type, have been developed by providing foils in the space between the relatively movable bearing elements. Such foils, which are generally thin sheets of a compliant material, are deflected by the hydrodynamic film forces between adjacent bearing surfaces and the foils thus enhance the hydrodynamic characteristics of the fluid bearings and also provide improved operation under extreme load conditions when normal bearing failure might otherwise occur. Additionally, these foils provide the added advantage of accommodating eccentricity of the relatively movable elements and further provide a cushioning and dampening effect.
The ready availability of relatively clean process fluid or ambient atmosphere as the bearing fluid makes these hydrodynamic, fluid film lubricated, bearings particularly attractive for high speed rotating machinery. While in many cases the hydrodynamic or self-acting fluid bearings provide sufficient load bearing capacity solely from the pressure generated in the fluid film by the relative motion of the two converging surfaces, it is sometimes necessary to externally pressurize the fluid between the bearing surfaces to increase the load carrying capability. While these externally pressurized or hydrostatic fluid bearings do increase the load carrying capacity, they do introduce the requirement for an external source of clean fluid under pressure.
In order to properly position the compliant foils between the relatively movable bearing elements, a number of mounting means have been devised. The most common practice, as exemplified in U.S. Pat. Nos. 3,366,427, 3,375,046 and 3,615,121, is to attach a rod or bar to one end of the foil which can then be retained in a slot or groove in one of the relatively movable bearing elements. Alternately, as exemplified in U.S. Pat. Nos. 3,382,014 and 3,809,433, a plurality of overlapping foils may be individually mounted on a foil base such as by spot welds. The base would then be frictionally held against one of the relatively movable bearing elements. Individual foils may also be fastened directly to one of the movable bearing elements as illustrated in U.S. Pat. No. 4,262,975. Further, a lip or projection at one end of the foil may be restrained in a slot or groove in one of the relatively movable elements. Examples of this type of mounting can be found in U.S. Pat. Nos. 3,511,544, 3,747,997, 3,809,443 and 3,382,014. Individual foils have also been mounted intermediate the ends thereof as described in U.S. Pat. No. 4,178,046.
In order to establish stability of the foils in most of these mounting means, a substantial pre-load is required on the foil, that is, the individual foils must be loaded against the relatively movable bearing element opposed to the bearing element upon which the foils are mounted. It has been conventional to provide separate stiffener elements or underfoils beneath the foil elements to supply this required pre-load as exemplified in U.S. Pat. Nos. 3,893,733 and 4,153,315.
Hybrid bearing support structures for rotating elements, that is, a structure combining two or more different types of bearings, have been known. An example is U.S. Pat. No. 3,951,474 which illustrates a fluid film lubricated compliant foil bearing disposed between two relatively rotatable concentric shafts near the midspan thereof with the ends of the two shafts supported, in one embodiment, by rolling contact bearings. Alternately, a hybrid system may comprise a rolling contact bearing and foil bearing supporting opposite ends of a rotating shaft. While the rolling contact bearing has virtually no radial movement allowable, the foil bearing is comparatively soft and allows for measurable radial movement. Thus, there can be some sway misalignment and hence uneven load distribution which can greatly reduce the load carrying capacity and the life of the foil bearing. There are other bearings situations also which can introduce such misalignment or bearing tilt.
SUMMARY OF THE INVENTION
In a bearing misalignment or tilt configuration, such as a hybrid system wherein opposite ends of a rotating shaft are supported by a rolling contact bearing and a foil bearing respectively, means are provided at the foil bearing to correct or minimize such misalignment and thus accommodate any rotor deflection or tilt which would result therefrom. Several embodiments are described to axially redistribute the load within the foil bearing in order to increase its load carrying capacity and extend its operating life.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional view of a hybrid bearing system including a foil journal having the foil bearing alignment of the present invention;
FIG. 2 is a sectional view of one embodiment of a foil journal bearing of the present invention;
FIG. 3 is a sectional view of an alternative embodiment of a foil journal bearing of the present invention;
FIG. 4 is a perspective view of the underside of an individual foil for the foil journal bearing embodiment of FIG. 3;
FIG. 5 is a sectional view of another alternative embodiment of a foil journal bearing of the present invention;
FIG. 6 is a perspective view of the underside of an individual foil for the foil journal bearing embodiment of FIG. 5;
FIG. 7 is a sectional view of yet another alternate embodiment of a foil journal bearing of the present invention;
FIG. 8 is a perspective view of the underside of an individual foil stiffener for the foil journal bearing embodiment of FIG. 7;
FIG. 9 is a sectional view of still another alternate embodiment of a foil journal bearing of the present invention;
FIG. 10 is a perspective view of the underside of an individual foil for the foil journal bearing embodiment of FIG. 9;
FIG. 11 is a sectional view of still yet another alternate embodiment of a foil journal bearing of the present invention;
FIG. 12 is a perspective view of the underside of an individual foil stiffener for the foil journal bearing embodiment of FIG. 11; and
FIG. 13 is a perspective view of the underside of an alternate individual foil for the foil journal bearing of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to FIG. 1, there is illustrated a hybrid journal bearing in which one end of the shaft 10 is supported by a rolling contact bearing 12 while the other end of the shaft 10 is supported by a foil bearing 14. The foil bearing 14 generally comprises a bushing 16 upon which mounted are a plurality of overlapping compliant foils 18. As is clearly shown, the plurality of individual overlapping foils are outwardly diverging towards the free end of the shaft 10. The centerline designation is used to indicate the rotational axis of the shaft 10 as supported by the rolling contact bearing 12 and also the centerline of the outer diameter of foil bearing bushing 16. The centerline designation ' is used to indicate the axis of the shaft 10 at rest at the foil bearing end thereof. The overlapping compliant foil 18 outwardly diverge at an angle with respect to centerline which is the same as the angle formed between centerlines and '. For purposes of illustration, this misalignment angle, which would generally be on the order of 0.064 degrees, is shown as greatly exaggerated.
As illustrated in FIG. 2, the plurality of overlapping foils 28 can be made outwardly diverging by providing an outwardly diverging conical surface 29 on the inner diameter of the bushing 26. With the outwardly diverging inner diameter 29 of the bushing 28, the foils 28 can be of the conventional type and would follow the contour of the inner diameter 29 of the bushing upon which they are mounted. In this manner the foils would outwardly diverge towards the free end of shaft 10.
While the embodiment of FIG. 2 permits the utilization of conventional foils, it does require forming, such as by machining of a slightly conical inner surface on the bearing bushing 26. The same effect, that is outwardly diverging foils, can be achieved with a cylindrical inner surface of the bushing as will be described with respect to the remaining figures of this application. A number of alternate embodiments of this type are illustrated in FIGS. 3-13.
FIGS. 3-6, for example illustrate achieving the outwardly diverging foil bearing 34 by the use of pads or shims on the underside of the foils. In the embodiment of FIGS. 3 and 4, shims 40 and 42 are affixed to the underside of the foils 38 which are mounted within bushing 36 around shaft 10. The first shim 40, closest to the outer end of the bushing 36 is of a lesser thickness than the outer shim 42. By way of example, shim 40 may have a thickness on the order of 0.001 inches while shim 42 may have a thickness of the order of 0.002 inches. While the foils 38 may be mounted within the bushing 36 by any conventional means, a mounting bar 39 is shown in FIG. 4 for purposes of illustration.
While the shims 40 and 42 illustrated in the embodiment of FIGS. 3 and 4 are of a constant thickness throughout their axial length, a refinement of this embodiment is illustrated in FIGS. 5 and 6. In this embodiment, the shims 40' and 42' increase in thickness along their axial length toward the free end of the shaft 10. Whereas in the FIGS. 3 and 4 embodiment the underside of the shims 40 and 42 are parallel to the underside of the foil 38, the underside of the shims 40' and 42' are parallel to the inner surface of the bushing 36. In both of these embodiments, the foils are mounted in the bushings without the benefit of any underfoil or foil stiffener.
In the embodiment of FIGS. 7 and 8, and also that of FIGS. 11 and 12, the outwardly diverging foil bearing is achieved with the use of underfoils or foil stiffeners. In these embodiments conventional foils can be uitilized, and it is the underfoil or foil stiffener which develops the outward divergence of the foils. FIGS. 7 and 8, for example, illustrate a foil journal bearing 44 which provides foils 48 mounted around the shaft 10 within the busing 46. A plurality of underfoils or stiffeners 50 are also mounted within the bushing 46 underneath the foils 48. A plurality of ribs 51 are formed on the surface of the stiffeners 50 presented to the foils 48 to provide the preload for the foils 48. As most clearly illustrated in FIG. 8, shims 52 and 53 are provided on the underside of the stiffeners 50 to develop the outwardly diverging configuration for the foil bearing 44. The relationship of the thicknesses of the shims 52 and 53 would generally be the same as the relationship of the thicknesses of shim 40 and 42 of the embodiment of FIGS. 3 and 4. It should be recognized that while the shims 52 and 53 are illustrated in FIG. 8 as each being of a constant thickness along their axial length, these shims could each have an increasing thickness along their axial length much the same as the shims 40' and 42' illustrated in FIG. 6 on the underside of foil 38'.
In the embodiment of FIGS. 9 and 10, the underside of foils 58, disposed between shaft 10 and bushing 56, are provided with ribs 60 of increasing thickness along the axial length thereof. Axially increasing thickness ribs 62 can likewise be provided on a stiffener 60 as illustrated in FIGS. 11 and 12. In this case, the stiffener will also have ribs 61 which are disposed within bushing 56 and would be in contact with the foils 52 which actually support the shaft 10.
An additional alternative foil configuration is illustrated in FIG. 13. In these embodiments, the foils 58' include ribs 60' on the underside thereof. The ribs 60' are of a uniform thickness along the axial length of the foils 58'. The outwardly divergence is developed by shims 40' and 42' on the underside of the foils placed over the ribs 60'. While the shims 40' and 42' are illustrated in FIG. 13 as having a tapered thickness along their axial length, in many cases it would be equally satisfactory for these shims to be of a constant thickness along their axial length and still provide the outwardly diverging foil bearing surface. Likewise, the ribs 62 on the underside of the stiffener 60 could be made of uniform thickness and shims, of either uniform thickness or varying thickness, placed over such uniform thickness ribs to achieve the same outwardly divering effect.
While a number of specific embodiments of this invention have been illustrated and described, it is to be understood that these are provided by way of example only and that the invention is not to be construed as being limited thereto but only by the proper scope of the following claims. | A bearing support structure for a journal bearing including a plurality of overlapping compliant foils mounted upon one of a pair of relatively rotatable members to form an outwardly diverging surface to support the other of the members. The outwardly diverging surface may be formed by varying thickness shims included along the axial length of the plurality of foils. | 5 |
CROSS-RELATED APPLICATION
This Application is a continuation-in-part of co-pending application Ser. No. 535,850 filed Dec. 23, 1974 now abandoned which is a continuation of Ser. No. 128,592 filed Mar. 26, 1971 now abandoned which in turn is a continuation of Ser. No. 659,924 filed Aug. 11, 1967 and now abandoned.
FIELD OF THE INVENTION
This invention is concerned primarily with the circumferential stressing of concrete pressure vessels such as may, for example, be employed in nuclear power stations or for the storage of gas or other medium under pressure.
BACKGROUND
It is known to suspend from the top of a structure around which wire is to be wound a mobile unit capable of holding a supply of wire in such a manner that said wire may be drawn therefrom, the unit being appropriately positioned and supported in relation to any selected circumferential trough or channel in or on the surface of the structure around which the wire is to be wound, so that, when the unit is carried around the structure at a desired speed and with one end of the wire securely anchored in the selected trough or channel, the wire will be wound around the structure.
In our prior U.S. Pat. No. 3,404,497 we have described a concrete pressure vessel or other concrete structure which is circumferentially stressed by means of prestressing wire or strands wound therearound under tension in a plurality of layers, such wire or strands being accommodated in circumferential troughs or channels which are provided in or on the outer surface of the vessel and serve to locate the layers of wire.
SUMMARY OF THE INVENTION
According to the present invention, there is provided apparatus for winding prestressing wire around a cylindrical vessel or structure, such apparatus comprising a platform or staging adapted to surround the vessel or structure and capable of being located at a selected height in relation thereto and a mobile unit which is supported on said platform for movement around the vessel and adapted to hold a supply of wire in such a manner that said wire may be drawn therefrom, the arrangement being such that with an end of the wire securely anchored to the vessel, movement of the unit therearound will result in winding of the wire around said vessel.
In order that the said invention may be clearly understood and readily carried into effect reference will now be made to the accompanying diagrammatic drawings.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a plan view of a platform or staging which is adapted to be erected around a pressure vessel and serves to support the wire winding equipment,
FIG. 2 is a section through the platform showing how the latter may be located in relation to a pressure vessel around which wire is to be wound,
FIG. 3 is a view taken in the direction of arrow A in FIG. 1 illustrating an arrangement of hoist ropes for the platform,
FIG. 4 is a plan view of the mobile wire winding unit,
FIG. 5 is a side elevational view on a larger scale of a tensioning unit employed in the assembly shown in FIG. 4,
FIG. 6 is a diagrammatic side elevational view of a modified tensioning unit,
FIG. 7 is an elevational view similar to FIG. 2 but showing two superposed arrangements of platforms and carriages in the course of winding wire simultaneously,
FIG. 8 is a section taken along line 8--8 in FIG. 4 showing the means for tilting the payout sheave,
FIG. 9 is a side elevational view of the means in FIG. 8,
FIG. 10 is a diagrammatic illustration similar to FIG. 9 of a modified arrangement for tilting the payout sheave, and
FIG. 11 is a diagrammatic perspective view of a guide arrangement for laying the wire in a groove in the vessel.
DETAILED DESCRIPTION
In the following description it will be assumed that it is required to wind prestressing wire around a cylindrical pressure vessel, the outer surface of which is, as described in U.S. Pat. No. 3,404,497 provided with a plurality of circumferentially extending troughs or channels for the reception of the wire.
Referring now to the drawings, 10 denotes such a pressure vessel while 11 denotes a substantially annular platform or staging which is so supported that it is capable of vertical movement upwardly and downwardly relatively to the vessel. The annular platform or staging is supported for vertical movement by means of a plurality of hoist ropes or cables 12 which are attached thereto at spaced points therearound and are passed around sheaves or pulleys 15 located at the upper ends of vertical columns or masts 13 disposed at appropriately spaced points around the outer periphery of said staging or platform. In the embodiment illustrated, it is proposed to support the platform 11 by means of three pairs of hoist ropes at 120° angular intervals around the periphery of the platform at stations X as shown in FIG. 1, and the ropes of each pair are arranged as illustrated in FIG. 3.
Referring to FIG. 3, it will be seen that a pair of ropes 12 which are attached to the platform through the medium of strain screws 14 are passed over the sheaves 15 mounted at the upper ends of the columns or masts 13 to a member carrying a sheave 16 around which a single hoist rope 17 passes, such rope 17 being passed around an appropriate sheave system and being coupled to a winch which is driven through the medium of an electric motor or other prime mover (not shown). The three motors or prime movers of the three winches are synchronized so that on operation thereof in one direction or the other the staging or platform will be raised or lowered while being maintained in a horizontal or substantially horizontal plane. If desired, electro-magnetic or other appropriate devices may be incorporated to ensure that the staging or platform will be maintained substantially level during movement. In order that the staging or platform may be located in any desired predetermined horizontal plane or at a predetermined height in relation to the pressure vessel, provision is made whereby the staging or platform may, on being moved into such predetermined position can be locked in place. To this end, all or certain of the columns or masts 13 will be provided at appropriately spaced intervals along their length with support blocks 18 (FIG. 2) while the platform 11 will be provided at each of an appropriate number of angularly displaced points with a projectable and retractable bearing bolt 19, such bolts being capable of being moved into and out of operative position by hydraulic cylinders 19a mounted on the platform wherein they will serve to cooperate with the appropriate support blocks 18 thereby to hold or lock the staging or platform. Additionally for the purpose of positively locating the platform 11, the latter is equipped at its inner periphery adjacent the wall of the vessel 10 with a plurality of hydraulically or pneumatically operated arms one of which is indicated at 20 in FIG. 2. As will be seen, the arm 20, which is pivoted at 21 on a member forming part of the platform sub-frame 22, is adapted to be moved angularly about its pivot 21 by means of a fluid-pressure operated cylinder 23 mounted on the platform thereby to bring a support block 24 carried on arm 20 into and out of a position wherein it will cooperate with the wall of a selected circumferential trough or channel around the outer surface of the pressure vessel 10. Since certain irregularities or tolerances will be present in the surfaces of the pressure vessel, provision will be made for adjustment of the block 24 on the arm 20 and also the upper end of the arm will preferably incorporate a resilient portion or section or an element which is capable of flexing so that despite irregularities in the concrete structure, the arm 20 may be caused to assume its correct operative position.
The arrangement above described is such that, when it is desired to position the platform 11 at a selected level around the vessel, the bolts 19 and the arms 20 will be moved into retracted or inoperative positions and the hoist motors will be operated to raise or lower the platform 11 as the case may be. In these retracted positions the bolts 19 and the support blocks 24 on the arms 20 will clear the support blocks 18 on the masts 13 and the outer surface of the vessel 10 respectively. On reading the selected level, the platform 11 will initially be positioned slightly above that level whereafter the bolts 19 and the arms 20 will be moved into their projected or operative positions. With the bolts 19 and arms 20 so actuated, the platform will then be lowered until the bolts 19 seat on the appropriate support blocks 18 and the support blocks 24 on the arms 20 engage the wall of the appropriate trough or channel.
At its inner periphery, the staging or platform 11 is provided with a plurality of upstanding support brackets 25 or the like which are spaced therearound and serve to support suitably housed or enclosed electrical conductors 26 from which power will be supplied to operate the wire winding unit hereinafter referred to.
Located on the staging or platform is a pair of I section rails 27 so arranged as to provide a circular track around the pressure vessel in a horizontal plane. The inner rail 27 serves to house and locate a drive chain 28 which is however so arranged as to remain stationary. Fixedly located on the upper surface of each rail 27 is an L section rail 29, the purpose of which will be hereinafter made apparent.
Disposed on the aforesaid track to travel therearound is what may be termed a train comprising two trolleys or carriages provided with running wheels or rollers 32 adapted to run on the running surfaces provided by the L section rails 29. Said trolleys or carriages are also equipped with guide roller 33 freely rotatable about vertical axes and adapted to cooperate with the vertical limbs of the rails 29, such arrangement providing lateral restraint and ensuring maintenance of said trolleys or carriages in their correct positions on the circular track. Located on the foremost trolley 30 is a hydraulic power unit or motor 34 in driving engagement with a sprocket 35 around which the aforesaid drive chain 28 is caused to pass. The output shaft of the motor 34 is drivingly coupled to sprocket 35 by belt 35a as diagrammatically shown in FIG. 4. Idler sprockets such as indicated at 36, 37, 38 are appropriately disposed in relation to the drive sprocket 35 in order to ensure that the drive chain 28 is appropriately looped around the latter. Preferably, the relative positions of the sprockets 36,37 will be adjustable in order to allow for maintenance of appropriate tension in the drive chain 28. As indicated above, the drive chain 28 is maintained stationary but upon operation of the hydraulic motor 34 on the leading trolley, the drive sprocket 35 will be driven thereby to cause the latter and hence the train to move along the chain 28 and around the track. The hydraulic motor 34 is reversible so that the drive sprocket can be driven in opposite directions and thereby the train can be driven in forward or reverse direction around the track. Alternatively, the chain 28 could be replaced by fixed teeth on the outside wall of the vessel or structure 10, the drive sprocket 35 engaging these fixed teeth.
Also located on the leading trolley or carriage 30 is a so-called payout sheave 39 around which the wire indicated at W will pass in its passage to the periphery of the pressure vessel, sheave 39 being rotatable about an axis which is adjustable or displaceable within limits as will be hereinafter explained. Located on the second trolley 31 is a wire tensioning unit 40 i.e. a unit which will apply tension to the wire to ensure that it will be wound around the vessel under a predetermined tension. Numerous means may be employed for applying the required tension but it is proposed to employ a unit such as is indicated in FIG. 5, such unit comprising two endless belts or chains 41, 42 disposed vertically one above the other so that the lower flight of the upper belt or chain 41 will be in contact with or closely adjacent to the upper flight of the lower belt or chain 42. The support frame or structure 43 for one of the belts or chains in the embodiment illustrated is so supported on floating mountings 44 as to be capable of a limited floating movement in a fore and aft direction. In addition, the support frames or structures of the respective belts or chains are coupled together by hydraulic ram means 45 so that the belts or chains may be urged towards and into contact with each other. The belts or chains 41,42 are equipped with pads of friction gripping material (not shown). The arrangement is such that the wire W will be led from a storage spool 50 longitudinally between the two belts or chains 41, 42 to the aforesaid payout sheave 39. The belts or chains are driven by hydraulic motors 51 and it will be appreciated that by appropriate extension of the hydraulic ram means 45, the friction gripping pads on the belts or chains 41, 42 will correspondingly frictionally grip the wire and cause the wire W to advance with the belts without slippage during winding operation. The belts or chains 41,42 are driven at a speed appropriately controlled in relation to the speed of travel of the trolleys or carriages 30,31 to result in the appropriate tensioning of the wire. In the embodiment illustrated in FIG. 5, the terminal sprockets at 46, 47 around which the respective belts or chains pass, are each coupled to a respective hydraulic motor whose speed is effectively controlled through the medium of two load cells which are arranged side by side and one of which is indicated at 48. Due to the fact that the tension unit floats on the mountings 44 i.e. is capable of fore and aft movement on mountings 44, and variation in tension on the wire will result in a displacement of the tensioning unit on the mountings, and in the transmission of a signal from the load cell 48 to a control system controlling the aforesaid hydraulic motors. The load cell may be any conventional transducer known in the art and including strain gages or the like for producing an electrical output depending on load. The control systems are in themselves well known and there is no necessity for further description herein. The control arrangement is such that it will be possible accurately to control the speed differential between the belts or chains 41,42 and the carriages or trolleys 30,31 so that the tension on the wire will be maintained at a predetermined value. The tensioning unit indicated above has the advantage that the passage of the wire is linear i.e. the wire is not curved or distorted nor is it subjected to unacceptable heating or any other contingency which may adversely affect it.
As indicated above while a tensioning unit such as is described above may be preferred, other devices may well be employed. For example, the wire can be passed between stationary pressure pads or the like 51,52 operated by jacks 53 or the like which cause said pads to grip the wire as it passes therebetween thereby to apply a predetermined tension thereto. In this case the wire is pulled through the pads whereas in the embodiment in FIG. 5, the belts or chains travel with the wire.
The storage spool 50 from which the wire is led through the tension unit is located on the second or trailing trolley or carriage 31 as shown in FIG. 4 and as indicated such carriage or trolley is also equipped with an operator's control cabin as indicated at 47 adapted to house control means for the carriages or trolleys and associated items of equipment and a seat or control position for an operator.
While it is envisaged that two trolleys or carriages 30,31 will be employed, it may be feasible merely to utilize a single trolley or carriage or alternatively three or more trolleys on which the wire supply means, the tensioning unit drive means, payout sheave and the necessary control equipment will be accommodated while allowing space for an operator.
With the apparatus so far described, when it is desired to wind wire into a selected circumferential trough or channel in a pressure vessel, the platform or staging 11 will be set at an appropriate level. Wire will be led from the supply drum 50 on the trolley or carriage 31 via the tensioning unit 40 around the payout sheave 39 on the forward trolley or carriage 30 and into the selected trough or channel where the end will be anchored in any appropriate manner. With the end of the wire anchored, the power unit 34 will be actuated to drive the sprocket 35 and thus to cause the trolleys or carriages 30, 31 to travel around the vessel. As the trolleys or carriages travel around the vessel, the wire W will be drawn from the supply drum 50 via the tensioning unit 40 and will be wound around the vessel. Due to the tensioning unit, the wire will be wound onto the vessel under a predetermined tension. As indicated in our prior U.S. Pat. No. 3,404,497 it is proposed to wind the wire in a plurality of layers in each groove as seen in FIG. 2. When the predetermined number of turns or layers of wire have been wound in a selected groove, the trolleys or carriages will be stopped and the end of the wire will be appropriately anchored, for example, by means of anchor plates, in the groove whereafter the apparatus may then be properly positioned in relation to another trough or channel in readiness for a further winding operation.
The payout sheave 39 performs two functions. Firstly it provides for the turning of the wire through 180° as seen in FIG. 4, and secondly it serves to adjust the pay-off height of the wire so that the strands will be correctly positioned in the trough or channel on the vessel. It is to allow for performance of the second function that provision is made for the before mentioned adjustment of the axis of rotation of sheave 39. The arrangement is such that as one complete passage of wire around the vessel is achieved, the sheave 39 will be tilted by an amount corresponding to the thickness of the wire so that while the point of entry of the wire onto the sheave 39 from the tensioning unit will remain at a constant level, the point of departure of said wire from the sheave will be either raised or lowered by an amount corresponding to the thickness of the wire so that on the next passage around the vessel, the resulting winding will be laid in side by side relationship with the preceding winding with no overlapping of said windings. By arranging for such adjustment of the payout sheave 39, any necessity for adjusting the height of the trolleys or carriages or of the tensioning unit during successive windings will be obviated and within certain limits, pay-off of wire at any required height may be achieved.
The control of the sheave may be effected by the arrangement shown in FIGS. 8 and 9. Therein it is seen that sheave 39 is supported on a bearing 59 on a cross member 60 whose ends are fixed to upright arms 61 secured on trunnions 62,63 which are rotatable in uprights 71 rigidly mounted on platform 30. The wire W passes from supply drum 50 through a hole on the axis of trunnion 62 and enters a groove formed on the periphery of sheave 39.
An indexing system acts on arm 61 to pivot the sheave 39 about the axis of the rotation of the trunnions 62, 63 in the uprights so that the exit point of the wire from the sheave will be vertically moved upon each revolution of the carriage while the entry point of the wire remains the same.
The indexing system in FIGS. 8 and 9 comprises a rotatable cam 64 mounted on the carriage 30, the cam having spaced projecting pins 65 equidistantly arranged thereon. An actuator 66 is fixedly placed on rail 27. When the carriage passes the actuator 66, the latter strikes one of the pins 65 on the cam 64 causing the latter to undergo rotation through a portion of a revolution. A drive chain 67 is driven by the cam 64 and the chain drives a pair of lead screws 68 in rotation a corresponding amount. Each lead screw supports a nut 69 which is pivotably affixed to a lower arm 70 and non-rotatable on its lead screw. The lower arm 70 is telescopically mounted on a respective arm 61 such that, when the lead screws 68 are rotated, the nuts will longitudinally travel a given amount on the respective lead screws and thereby cause arms 61 to pivot with trunnions 62 and 63 in the uprights to produce a corresponding tilting of cross member 60 and sheave 39 carried thereon. The spacing between the projections 65 on the cam 64 is correlated with the pitch on the lead screws and the diameter of the wire so that the sheave will tilt to raise the wire by an amount equal to its diameter once for each revolution of the carriage around the vessel whereby the wire will be laid in superposed rows in the grooves on the vessel as shown in FIGS. 2 and 7. At the end of a winding operation when the wire has reached a topmost location in the particular groove, the cam 64 is driven in the opposite direction either manually or by driving the chain 67 externally until the sheave 39 has reached its initial position and is now ready to lay another line of superposed rows of wire.
FIG. 10 shows a modification of the indexing system in which a hydraulic cylinder system is employed instead of the traveling nuts and lead screws. The sheave 39 is supported on cross member 60 as before, and the cross member 60 is fixed to upper arms 61 secured to trunnions 62 and 63. The cross member 60 is pivotably supported at 80 by the piston rod of a hydraulic cylinder 81 which is actuated to move cross member 60 in steps to tilt sheave 39 and successively wind the wire in superposed rows as before. A trip mechanism is employed to operate the cylinder 81 and comprises a fixed bracket 82 secured to carriage 30 and carrying a magnet element 83. A fixed member 84 is secured to rail 27 and produces an electrical output signal which is received by electrovalve 85 which in turn operates a fluid pressure source 86 to admit pressure fluid to cylinder 81 in a given amount to tilt the sheave 39 a corresponding amount to raise the wire by an amount equal to its diameter once for each revolution of the carriage around the vessel whereby the wire will be laid in superposed rows in the grooves on the vessel. At the end of a winding operation when the wire has reached a topmost location in the particular groove, a signal is fed to electrovalve 85 to cause it to return to its initial position such that fluid will return to the pressure source 80 and cylinder 81 will lower the sheave to its initial position so that it is now ready to lay another line of superposed rows of wire.
It may be mentioned here that it is possible to incorporate a sensing device which would travel in the trough or channel in the vessel and sense any irregularities or tolerance in the latter, such device being effective to transmit a signal to the control means for the sheave so that the position of the latter will be adjusted to ensure correct laying of the wire strand.
In order to ensure that the wire is laid correctly in each groove, it is fed, after passing around the payout sheave 39, through a guide arrangement shown in FIG. 11 comprising two cooperating guide rollers 90 which serve to guide the wire onto the vessel. The position of the rollers 90 is adjustably controlled by a hydraulic cylinder 91, the hydraulic fluid supply of which is controlled by an electrovalve 92 operated by position transducer 93. The transducer 93 responds to pressure applied by pivotal arm 94, the latter being biassed by a spring 95 and carrying at its free end a sensing roller 96 positioned to run in the trough or channel in the pressure vessel on the wound wire. The guide rollers 90 follow the movement of the sensing roller 96 in order to correctly lay the wire in the groove.
It will be appreciated that the apparatus above described may be modified in many respects. Clearly the locking of the platform 11 in any selected position may be effected in many ways other than that hereinbefore described and illustrated. Furthermore, as already mentioned, the number of trolleys or carriages to support the wire supply, the tensioning unit drive means, payout sheave and the necessary control mechanism may be varied. In addition, instead of providing an annular track-supporting platform such as 11 which is raised and lowered by means of a plurality of hoist ropes or cables such as hereinbefore described, any other arrangement of hoist ropes or the like may be employed or it may be desirable to provide some construction wherein such a platform is supported by a plurality of jacks or the like, by means of which raising or lowering of said platform may be effected. The jacks may be located above or below the platform in which former case it would be necessary to provide some structure from which the jacks would be suspended.
In another embodiment as shown in FIG. 7, there are provided upper and lower platforms movable relatively to each other, each platform carrying a respective wire-dispensing mobile unit so that wires are placed simultaneously in two grooves in the vessel.
It may be mentioned here that it may be desirable since an operator stationed in the cabin 47 at the rear of the trolley or carriage 31 will be unable to see the forward part of the leading trolley or carriage 30, to provide a closed circuit television screen in the cabin 47 so that the operator will be able to observe the whole equipment during operation.
While the apparatus described above is intended primarily for the winding of prestressing wire onto a concrete vessel, it may also be utilized to remove loose or tensioned wire, for example, in the case of breakage of the wire or of a fault in winding thereof. In the case of a breakage, the loose end of the wire may be taken back around the payout sheave, through the tensioning device of the supply drum or spool with the spool rotating in the reverse direction and with the trolleys or carriages driven in reverse the wire may readily be wound back on the spool. In the event of a fault in winding, e.g. in the event that one winding is laid over the top of another, by reversing the direction of rotation of the wire drum and reversing the direction of travel of the trolleys or carriages it will be possible to rewind or take off the wire from the vessel back to the point of the fault while still maintaining the tension on the wire and one of the coils already wound. With sufficient wire rewound and the fault remedied the apparatus may then be operated normally to proceed with further winding. | A temporary platform encircling a concrete pressure vessel carries endless rails on which a mobile unit runs. The unit has a supply drum from which is drawn pre-stressing wire anchored at its free end in one of many channels in the outside wall of the vessel. The wire leaves the unit via a tensioning unit and a payout sheave both carried by the mobile unit. Hoist ropes fixed at intervals around the platform and connected to winches lift and lower the platform to locate the sheave at the level of each channel in turn. | 4 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to dental treatment equipment and root canal dental instruments. Specifically, it relates to a self-contained root canal dental instrument that combines the operations of a root canal spreader, a root canal condenser, and a root canal filling material heater.
2. Description of the Background
A need has existed for a long time for a way to reduce the time involved in filling a prepared root canal of a human tooth with the filling material. The time involved being used in the continual pick up of separate dental tools for spreading filling material, condensing the filling material, and the alternate heating and reheating of the filling material, during the spreading and condensing operations. Equally important is the complete adaptation of the filling material to secure a hermetic seal against leakage.
Gutta percha is the usual material that is used for filling root canals. Gutta percha, as with other root canal filling materials, must be spread and condensed in the root canal and heated to improve its flow and adaptation qualities. Gutta percha material deforms when warmed and compressed. It becomes pliable at 25 to 30 degrees Celsius, it becomes soft at 60 degrees Celsius, and it decomposes at 100 degrees Celsius. At such temperatures a phase transition occurs allowing the gutta percha to flow into the many irregularities of the prepared root canal, thus allowing for a three-dimensional obturation and sealing to occur. Such a three-dimensional obturation and sealing is necessary for success in root canal therapy.
When the filling material is softened, it is then compressed into the numerous aberrations of the root canal in order to effectively seal the root canal cavity. The compressing of the filling material in the prior art is performed by using root canal filling spreaders and filling condensers of a variety of sizes and with several handle designs (both long and short). The root canal filling spreaders and filling condensers deform the filling material under heat and stress and allow compaction and condensation that leads to the lateral spreading to fill the voids in the root canal. As bits or points of filling material are placed into the root canal, as hereinbefore described, the heated, spreader tool is forced between the bits or points of material after each such insertion which pushes and compacts the filling material vertically to the apex of the root canal and, concurrently, laterally. The tool is pressed manually and also rotated side to side to achieve the spreading of the material. It also acts as a heat sink cooling down quickly for controlled concentration.
The filling spreaders and condensers of the prior art for root canal work are generally of stainless steel or chromium plated brass. The filling spreaders are smooth, flat ended and slightly tapered. For the most part, the prior root canal filling spreaders and condensers had to be heated over a flame, such as over the flame of a Bunsen burner, and then passed into the mouth of a dental patient and then into the prepared root canal where the filling material has been placed. Such tools had to be transported quickly from the Bunsen burner into the mouth of the patient and into the tooth and the root canal and against the cold mass of filling material. There is the constant danger of burning the patient about the mouth each time a heated dental tool is moved from the flame to inside the mouth. Moreover, if it becomes too hot the filling material will stick to the dental tools of the prior art.
A few prior art attempts have been made to provide for heating the tools while in the mouth. However, problems have been encountered. For example, the tips have been bulky and too wide. Also, the tips do not wedge lock into place and 360 degree rotation has been encountered which reduces the effectiveness of the condensing operation. Further, the heat control has been unreliable, the system having as many as ten dial settings which required an assistant or required the dentist to stop the condensing operations to attempt to make a better heat selection or to interrupt the heat process. In addition to the above problems, the filling material sticks to the surface of the so called heat control tools, and the system has a cumbersome power box and control means.
U.S. Pat. No. 4,392,827 issued Jul. 12, 1983 to the inventor herein proposes a solution in the form of a self-contained dental instrument inclusive of a combination spreader, condenser, and a filling material heating unit, each of which is alternately and/or concurrently useable while inserted within the root canal structure of a patient. The '827 invention generally includes a plugger component or “tip” which combines the functions of a spreader, a condenser, and a material heating unit; a handle component affixed to the plugger component; a power supply component for producing heat; and a transmission component for transmitting heat produced by the power supply component to the material heating unit of the plugger component. The transmission component has a conveniently located finger operation switch to interrupt the power supply and cut off the flow of heat. A variety of plugger components are provided in a range of sizes to fit the range of internal sizes in different parts of the root canal. The '827 invention reduces the number of entries into the mouth that are necessary during a root canal filling, and also provides for inducing the heat for the tool after the tool is in the tooth at the root canal cavity. The plugger unit or tip is used to heat the filling material and then laterally condense or press the filling material into the root canal areas. Thereafter, the tip may also be used to maintain the heat or reheat the filling material and to vertically condense the filling material into the root canal in a compacting type of operation. While the use of the filling condenser to vertically condense the filling material is often referred to as a plugging operation, the use of the filling spreader to laterally condense the material before the vertical condensing is is also a part of the total plugging operation. Additional bits or points of filling material are placed into the root canal cavity and then followed by the spreading and condensing operations described hereinbefore for the filling spreader and condenser root canal tools. These operations are continued until the required amount of filling material plugs and seals the root canal in accordance with dental art.
The above-described invention eliminates the risk and expense of the many repeated tool exchanges and reheating operations. However, the device itself has proven expensive. The '827 device made use of a tip which housed both heating element and resistor. The presence of the resistor within the tip increased the cost. More significantly, the tip could not be sterilized due to the resistor.
It would be greatly advantageous to provide a modified design in which the resistor is moved out of the tip and into the hand piece, along with other design modifications, to thereby make the instrument more cost effective for the dentist and sterilizable for infection control requirements.
SUMMARY OF THE INVENTION
It is, therefore, an object of the present invention to provide A self-contained root canal dental instrument that combines the operations of a root canal spreader, a root canal condenser, and a root canal filling material heater in a less expensive and easier to replace plugger unit.
It is another object to accomplish the foregoing by incorporating a heating resistor element in the hand piece rather than the condenser tip, thereby making the tip removable and sterilizable. This in turn satisfies the infection control requirements of the Food and Drug administration, and makes the use of the instrument much more convenient and cost effective for the dentist.
It is a necessary object to accomplish the foregoing by employing a different heating circuit within the hand piece, the heating circuit being adapted to provide a proper impedance (inclusive of parallel resistances, proper length and proper amounts of copper flashing) to allow correct heating within the tip.
It is a further object to provide an improved insulation system for the tip described above.
It is still another object to replace the NiCad batteries and recharger as suggested in U.S. Pat. No. 4,392,827 issued Jul. 12, 1983 to the inventor herein with conventional alkaline batteries, and to adapt the electronics and housing accordingly.
BRIEF DESCRIPTION OF THE DRAWINGS
Other objects, features, and advantages of the present invention will become more apparent from the following detailed description of the preferred embodiment and certain modifications thereof when taken together with the accompanying drawings in which:
FIG. 1 is a pictorial view of a self-contained root canal heated condenser dental instrument according to the present invention;
FIG. 2 is a side view of the instrument of FIG. 1;
FIG. 3 is an enlarged cross sectional view on line 6 — 6 of FIG. 2;
FIG. 4 is an enlarged cross sectional view on line 7 — 7 of FIG. 2;
FIG. 5 is an enlarged side perspective view of the tapered tip 26 of plugger component 16 .
FIG. 6 is a side partial cut away view of the handle component 17 of dental instrument 15 .
FIG. 7 is a side cross-section of the handle component 17 of dental instrument 15 .
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Gutta percha is a high molecular weight polymer trans polyiosprene. If it is heated above 65° C. it becomes amorphous. It is cooled at 0.5° C. per hour and will slowly recrystallize in the beta form which is the form of dental gutta percha usage. Gutta percha may be applied by the lateral condensation technique. This is a compression of solid gutta percha cones together and adaptation to the root canal walls.
Referring now to the drawings and particularly to FIG. 1, an improved self-contained root canal heated condenser dental instrument 15 is shown for practicing the lateral condensation technique. The instrument 15 of FIG. 1 includes a plugger component 16 and a handle component 17 .
FIG. 2 is a side view of the instrument 15 of FIG. 1 with internal components indicated by dotted lines. Inside the handle component 17 is a power source 18 and a heat transmission coupling 19 . The structure of each of the plugger component 16 , handle component 17 , power source 18 , and a coupling 19 for plugger component 16 as described hereinafter.
The power source 18 must be sufficient to provide the control heat as hereinafter described. Preferably, the power source 18 comprises a pair of standard alkaline AA batteries that fit inside the end of the handle component 17 at the distal end from the plugger component 16 . A screw-on end closure 44 with terminal spring 5 A provides an easy access means for inserting the power source 18 . When screw-on end closure 44 is installed, a conductive path exists from one output terminal of the power source 18 through terminal spring 5 A and handle component 17 (via a conductive metal trace or a conductor wire housed therein). The instant use of ordinary alkaline batteries rather than NiCad batteries and recharger helps to keep the unit cost low.
The plugger component 16 is preferably formed as two pieces including a tapered tip 26 joined to an extended portion 30 . The tapered tip 26 consists of a main resistive core 20 with a Teflon coating 22 , both as shown in FIG. 3, which is an enlarged cross sectional view on line 6 — 6 of FIG. 2 . Resistive core 20 may be formed of conventional ceramic resistor material.
Referring to FIG. 2, the Teflon coating 22 extends from the pointed end of tapered tip 26 to the top 28 of the tapered portion 26 . The Teflon coating 22 covers both the end 24 of the core 20 as well as the tapered portion 26 . The extended portion 30 is a more or less uniform diameter for the balance of the extension, as hereinafter described, to the an end that inserts into the heat transmission coupling 19 . The extended portion 30 is bent in a convenient goose neck like configuration to a straight portion 32 that inserts into the aforementioned coupling 19 . It is to be understood that the extended portion 30 may be maintained straight, bent at a right angle, or formed into any other configuration, and all such variations are within the scope and intent of the invention. The plugger component 16 includes tapered portion 26 (core 20 and the Teflon coating 22 ), as well as the extended portion 30 and straight portion 32 .
FIG. 4 is an enlarged cross sectional view of the extended portion 30 of plugger component 16 along line 7 — 7 of FIG. 2 . The extended portion 30 is insulated 74 about the periphery, as shown in FIG. 4 . In addition, a central layer of insulation 76 separates two conductive leads 78 a and 78 b . The outer insulation 74 , central layer of insulation 76 , and conductive leads 78 a and 78 b run the entire extent of the extended portion 30 from the interface with the tapered portion 26 to a point 36 just clear of chuck 38 . The outer insulation 74 is preferably a layer of Pyre-ML, which is an enamel used in the motor industry for coating electrical windings. The insulation 74 also provides protection against burning of parts of the mouth of a dental patient while root canal work is being done.
In accordance with the present invention, the tapered tip 26 is bonded to extended portion 30 at a junction 28 using Master Bond® Epoxy No. EP42Ht. This particular epoxy has been tested under a force gage at 50 lbs. until shearing took place. Thus, using the International standard for hypodermic needles ISO 7864, it has been determined that the tapered tip 26 can withstand an acceptable push-out force of at least 9.25 lbs. This bonding material also acts as a heat shield to confine the heat to the tapered portion 26 and to keep the extended portion cool. This is an important safety feature and it allows almost immediate cold compaction of the root canal filling material.
FIG. 4 is a cross-section of the extended portion 30 , and FIG. 5 is an enlarged side perspective view of the tapered tip 26 of plugger component 16 , both showing the internal conductive leads 78 a . Tapered tip 26 is bonded such that both conductive leads 78 a and 78 b make electrical contact with the resistive core 20 of the tapered portion 26 . Heating at the tapered portion 26 is accomplished with the insulated lead 78 a extending downward through the extended portion 30 to the tapered portion 26 , and with identical return 78 b . Both conductive leads 78 a and 78 b are insulated. This way, application of power from power source 18 through the conductive leads 78 a and 78 b and into the resistive core 20 generates heat therein which is quickly transmitted outward through the Teflon coating 22 . The Teflon coating 22 prevents the root canal filling material from sticking or adhering to the plugger component 16 at the area of contact during a root canal treatment. The heat in the core 20 will readily pass through the Teflon coating 22 to heat the root canal filling material during treatment.
The extended portion 30 of plugger component 16 may be provided in a variety of sizes and shapes for use in root canal work that may vary from near the front of the mouth to the very back of the mouth. For example, a long neck exterior portion 40 facilitates reaching the back teeth.
FIG. 6 is a partial cross-section showing the plugger component 16 coupled into the end of the handle component 17 with the conductive leads 78 a and 78 b extending into coupling 19 . This is accomplished by inserting the plugger component 16 into the end of the handle with leads 78 a and 78 b inserted into mating receptacles in coupling 19 , and then anchoring the plugger component 16 therein by screw-tightening a chuck 38 . Once connected, one of the leads 78 b completes an electrical circuit with power source 18 through a balance resistor 21 which allows control over the amount of heat dissipated by the plugger component 16 . The other conductive lead 78 a is connected to one terminal of switch 50 . The combined conductive leads 78 a and 78 b essentially make a loop down to the end of the plugger component 16 , starting as aforementioned at switch 50 , running out through the extended portion of plugger component 16 , around the gooseneck bend of the extended section 30 , then down the tapered section 20 , then back through the gooseneck bend of the extended section 30 , through the straight section 66 and making the aforementioned contact with the opposite terminal of power source 18 .
FIG. 7 is a cross-section of the handle component showing the chuck 38 for connecting and holding the plugger component 16 in place. The chuck 38 is affixed to the handle component 17 at an aperture in the handle component 17 through which the end of the plugger component 16 passes to insert into the heat transmission coupling 19 . The handle component 17 , in addition to serving as the means for a dentist to hold and use the root canal dental instrument 15 manually, also serves as a case or housing for the power source 18 and the heat transmission coupling 19 . The chuck 38 is threaded onto the distal end of handle component 17 , the tightening or which secures the plugger component 16 (not shown) in place.
The power source 18 aforementioned is biased at the leading end by another terminal spring 5 B, terminal spring 5 B also serving as a conductive path to a spacer switch 50 . Depression of the spacer switch 50 further completes the conductive path to the heat transmission coupling 19 as hereinafter described. The switch 50 is preferably a push-button activator pad positioned for thumb operation at the neck of the instrument 15 and easily depressed while holding the root canal dental instrument 15 by the handle component 17 . A variety of suitable switches are readily available for use as spacer switch 50 . The spacer switch 50 is set in a normally “off” position and depressing it with the finger, as hereinbefore described, turns the switch “on” to provide power to the heat transmission coupling 19 . The switch 50 is spring-loaded and it automatically returns to the “off” position when the finger is removed or lifted. The switch 50 is connected in series between the power source 18 via terminal spring 5 B and through a conventional resistor 21 , resistor 21 in turn being connected through the handle component 17 (either directly or by an internal conductor) to the opposite polarity terminal spring 5 A. The resistor 21 is an integral part of the heat transmission coupling 19 , such that when the end of the plugger component 16 is inserted into the heat transmission coupling 19 , the resistance of resistor 21 is in series with that of tapered portion 16 , and the two resistances are balanced to provide appropriate heating of the tip as desired. Thus, upon depression of spacer switch 50 approximately 3 volts of power is applied across the series-coupled heat-dissipating core 20 of tapered portion 16 and the resistor 21 , and heat is generated thereby at the tip. The leads of resistor 21 and all other series conductors as necessary are preferably formed from nickel-chrome wire. A conventional 1.4 ohm resistor makes a suitable resistor 21 . A layer of insulation encircles the immediate area around the resistor 21 . The insulation is preferably a section of polyester shrink tubing with an average wall thickness of 0.00025 inches. Heat transmission coupling 19 is open at the other end to surround the straight portion 32 of the plugger component 16 . The heat in the heated tapered portion 26 passes through the Teflon coating 22 for use in heating the root canal filling material, as hereinbefore described, so that the root canal dental work can be performed.
Given the above-described configuration, the heat in the heated tapered portion 26 has been found to vary between 150 to 250 degrees Fahrenheit. This is a higher heating capacity when compared to the device of the '827 patent. During clinical testing the heat resulted in thermo-softening of the gutta percha in approximately three seconds. Compacting was then easily accomplished to provide excellent results. Moreover, the utilization of standard AA batteries, and the placement of the resistor 21 inside the handle unit have greatly reduced the cost of the device. Further, inasmuch as the resistor 21 resides within the handle rather than the plugger component 16 , the entire plugger component 16 can now be removed and sterilized. This is extremely important inasmuch as the Food and Drug administration and Occupational Safety and Health administration require adequate sterilization to control infection. In clinical testing the instrument 15 has been found to be easy to use, consistent in both heating and compaction, and generally improving of the quality of root canal fills.
Having now fully set forth the preferred embodiments and certain modifications of the concept underlying the present invention, various other embodiments as well as certain variations and modifications of the embodiments herein shown and described will obviously occur to those skilled in the art upon becoming familiar with said underlying concept. For example, the range of sizes of the plugger component 16 may provide the range of lengths of the exterior neck 40 , as mentioned hereinbefore, and may also provide a range of diameters at the small end of the tapered portion 26 . The range of these small end diameters may begin with a very small diameter of less than one-half millimeter that is measured over the end of the core 20 and its Teflon coating 22 . It is to be understood, therefore, that the invention may be practiced otherwise than as specifically set forth in the appended claims. | A self-contained root canal dental instrument that combines the operations of a root canal spreader, a root canal condenser, and a root canal filling material heater in a less expensive and easier to replace plugger unit. A different heating circuit using balanced resistor elements in both the hand piece and the tip makes use of the instrument more cost effective for the dentist. The instrument combines a sterilizable condenser tip with the capability of achieving the correct heating temperature via standard AA alkaline batteries. | 0 |
TECHNICAL FIELD
[0001] This invention relates to a ribbon curling machine and more particularly to both a hand operated ribbon curling machine and an automatic ribbon curling machine for producing a multiple curled ribbon decorative product where the ribbons overlie each other and are attached together. In some embodiments the curled ribbons are attached to a self sticking backing card or a bow or a display holding card or the like.
BACKGROUND OF THE INVENTION
[0002] As is known to those skilled in this technology, there are sundry ways in which to curl ribbon of the type that are typically used to decorate packages, flowers/cookie baskets and the like. One of the more arcane methods of curling is by sliding the ribbon over a knife-edge or any other object where the ribbon slides over a friction surface. For example the simple operation of sliding the ribbon over the edge of ordinary pair of scissors causes the ribbon, be it paper or plastic, to curl. This obviously has limitations, such as being slow, typically done for a single ribbon, and in the more common usage the practice was to curl the end portions of a typical decorative bow. Other types of curling has been done by hand-held curling tools as those described In U.S. Pat. Nos. 5,400,452 granted on Mar. 28, 1995; 5,564,145 granted on Oct. 25, 1996; 5,407,417 granted on Apr. 18, 1995 to Fredric Goldstein, one of the joint inventors of this patent application. Obviously, like the scissors described above, the curling tools disclosed in the immediately aforementioned patents all would require tedious curling and assembly of the curled ribbon strands.
[0003] In more recent years, the curling of the ribbon has become automated where a drawing apparatus draws the ribbon to be in frictional engagement with an edge to impart a curl to the ribbon and stripping mechanism that permits the mass production of the curled ribbon which can then be utilized for different types of applications. Examples of this type of mass produced curled ribbon is disclosed in U.S. Pat. Nos. 5,518,492 granted on May 21, 1996, 5,711,752 granted on Jan. 27, 1998 and 5,916,081 granted on Jun. 29, 1999 to Fredric Goldstein, a co-inventor of this patent application.
[0004] Also, we are aware of other machines that has the ability of making a curled product that has certain similarities to the end product of this invention and is made by an entirely different method. In one instance, a reciprocal sliding mechanism includes a clamp that holds a ribbon while it is drawn over a stapling device. The ribbon is laid over itself to form a stack of curled ribbons and a stapling device staples the ribbon to a backing card and the cycle is repeated.
[0005] This invention is primarily concerned with the curled ribbon that is packaged in one or a number of configurations including the configuration as shown in FIG. 1 of this patent application (curly ribbon). As noted therein, this curled ribbon ribbon product has four (4) curled ribbons 2 each of which are stapled in the center via staple 4 . This makes eight (8) strands of curled ribbons 3 emanating from staple 4 . Obviously, when a given length of ribbon is attached intermediate the ends of the ribbon by a staple, the portions of the ribbon emanating from the staple forms two (2) strands. In this end curly ribbon product card 5 and ribbons 2 are stapled together. The card which is designed to hang in a display rack may include one surface (not shown) coated with a glue and a paper cover that is removable to uncover the glued surface for sticking to a package and the front surface may include indicia, such as a logo, price, etc. Obviously, in other embodiments the card may be replaced by or made complementary to other devices or objects such as a bow, ribbon, string etc. It obviously should be understood that the FIG. 1 end product is simply one example of an end product of a curly ribbon product. The end product could include as many strands as desired, and it is typical that more than eight (8) strands are formed to make-up the end product.
[0006] In one embodiment of this invention, the apparatus for making this product is portable and hand-operated and in an other embodiment of this invention, the product is automatically produced. It will be appreciated that in both embodiments, the ribbon is wrapped around a drum or rotor as it is rotated about an axis either by hand or a motor and that at discreet locations on the drum are provided mechanism for clamping the ribbons onto the drum, stapling the ribbons and card together and cutting the ribbons in another appropriate location. Obviously, the curled ribbon for some decorative purposes are affixed at an intermediate portion and for others they are affixed at the end.
[0007] In one preferred embodiment of this invention, a hand operated drum, reel or disk (hereinafter referred to as a drum) mounted for rotation and includes a handle attached to the drum for causing the rotation. This embodiment also includes a number of posts for holding a number of spools of ribbon, an equal number of guide posts for each of the spools, an equal number of curing clamps where the ribbon is placed in frictional engagement or contact to impart the curl thereto and a single guide post where all the ribbons are accumulated in such a manner that a portion of the ribbon is laid over other portions to form a stack to allow clamping with a single clamp. The drum includes stations to hold the combined ribbons with the use of an alligator clamp, and predetermined stations, one to staple the ribbons together and another to cut the ribbons. A card holder mechanism may be employed at the stapling station where the ribbons and card are simultaneously stapled together.
[0008] In another embodiment of this invention, an automated machine mass produces the entire package automatically once the machine is initially threaded. In this embodiment and according to this invention, a clamping mechanism including a pair of jaws judiciously clamps the then curled ribbon to the drum after being curled, the clamp releases the processed ribbon once the drum grasps the ribbons and sequentially re-clamps the next to be processed ribbons to continuously and cyclically produce an entire finished product. Also in accordance with this invention, this automated machine judiciously staples and judiciously cuts the curled ribbons in the proper sequence to produce the end product.
[0009] The advantages of utilizing a drum as taught by this invention and without limitation are as follows:
[0010] 1) the drum provides a compact drive system, more compact than heretofore known systems, making it possible to have a machine which requires minimal space, and in the portable unit, it can fit on an ordinary kitchen table or the like;
[0011] 2) the strands are inherently stacked together in the process of being pulled, unlike sets of wheels which would have to guide the 12 strands, for example, upon each other, which is critical when stapling or attaching the ribbon strands to a card;
[0012] 3) the drum obviates the need of sets of wheel or roller drive systems and the necessity of synchronizing the wheels and rollers in these types of systems and avoids the potential of “looping”;
[0013] 4) the drum, obviously, can increase the number of strands simply by increasing the number of revolutions in a cycle;
[0014] 5) because the ribbon wraps around itself on the drum the ribbon eventually secures itself to the drum and the clamp for originally clamping ribbon to the drum is released. Thus reduces the drag on the drum reduces as the rotation continues. This obviates the problems of adverse release and tearing of the ribbon in heretofore known systems. Also, the drum inherently requires less power in the drum and clamp to operate than these heretofore known systems; and
[0015] 6. the system using the drum always ends in the starting position for the next set of strands avoiding the necessity of repositioning the mechanism to begin the process.
[0016] In another aspect of this invention, the amount of curl can be controlled by selecting the proper discharge angle that the ribbon makes relative to the surface where the curl is imparted. Typically, the more acute the angle and hence the amount of drag or friction imparted to the ribbon as it is makes contact with the member imparting the drag or friction, the greater the degree of curl in the ribbon. This is the case no matter what the material the ribbon takes. This feature significantly allows the user to decide the overall size and shape of the curled ribbon product, whereby acute angles provides a more compact curled bow while lesser acute angles provides larger more flowing curls. When producing the curled ribbon product by an automated machine the curling device of this invention allows for consistency and flexibility in production.
SUMMARY OF THE INVENTION
[0017] An object of this invention is to fabricate a curled ribbon end product either manually or automatically by winding a plurality of ribbons around a rotating body and simultaneously imparting a curl thereto and then affixing the ribbons to another member and cutting the ribbon at different locations on the rotating body.
[0018] A feature of this invention is to provide a hand operated machine for making curled ribbons and attaching a plurality of ribbons taken from spools of ribbons to a clip or bobbin that is inserted into a rotatable drum that is rotated about an axis as by a handle mounted on the drum to draw the ribbons over a curling mechanism and which drum includes different stations for stapling the ribbons to each other and/or a card and for cutting the curled stapled ribbons.
[0019] Another feature of this invention is to provide a machine for automatically curling ribbons, attaching the curled ribbons to the drum of the machine, stapling the curled ribbons together at one station of the drum and cutting the ribbons at another station of the drum for producing a decorative piece. It will be appreciated that unless the ribbon upstream of the cutting or serving device is clamped prior to cutting, the ribbon will become disengaged from the drum and disrupt the cycle.
[0020] Another feature of this invention is to provide a curling device for imparting a curl to the ribbon that includes mechanism for changing the exit angle that the ribbon makes with the curling mechanism to control the curl characteristics of the ribbon.
[0021] Another feature of this invention is to provide a clamp that comprises automated fingers or jaws that are Controllable to temporally clamp, release and re-clamp a plurality of ribbons wound around a rotating drum.
[0022] Another feature of this invention is to provide an automatic machine for mass producing decorative curled ribbons by curling each of a number of ribbons and then combining and processing the combined ribbons through a number of sequential operations including the steps of winding the plurality of ribbons around a drum after being curled, affixing the curled ribbons to a card having a glued backing with the use of an automatic card feeding and stapling mechanism, an anvil, separately cutting the assembled card and curled ribbons that are attached to the card and releasing the assembled unit from the machine.
[0023] Another object of this invention is the method for producing a decorative multi-colored curled ribbon end product from a continuous supply of different colored uncurled ribbons including the steps of combining the different colored ribbons, stapling and cutting thereof.
[0024] Another feature of this invention is to provide a method that cyclically produces a curled ribbon product by the steps of providing a rotating drum, a clamp for clamping a plurality of ribbons which may be of different colors to a the drum until the ribbons are self-supported to the drum and then releasing the clamp from the ribbons, re-clamping the plurality of ribbons, affixing the ribbons together and then cutting the affixed ribbons in one cycle so as to provide a continuous process for mass producing the end product without the necessity of manually feeding the machine after the initial feed.
[0025] A still further object of this invention is to teach a system for making curled ribbon product that is characterized as being simple and inexpensive to use and manufacture as well as affording the following advantages:
[0026] 1) a compact drive system, more compact than heretofore known systems is attained, making it possible to have a machine which requires minimal space, and in the portable unit, it can fit on an ordinary kitchen table or the like;
[0027] 2) the strands are inherently stacked together in the process of being pulled, unlike sets of wheels which would have to guide the 12 strands, for example, upon each other, which is critical when stapling or attaching the ribbon strands to a card;
[0028] 3) it obviates the need of sets of wheel or roller drive systems and the necessity of synchronizing the wheels and rollers in these types of systems and avoids the potential of “looping”;
[0029] 4) it increases the number of strands simply by increasing the number of revolutions in a cycle;
[0030] 5) because the ribbon wraps around itself on the drum the ribbon eventually secures itself to the drum and the clamp for originally clamping ribbon to the drum is released. This reduces the drag on the drum reduces as the rotation continues. This obviates the problems of adverse release and tearing of the ribbon in heretofore know systems. Also, the drum inherently requires less power in the drum and clamp to operate than these heretofore known systems; and
[0031] 6. the system always ends in the starting position for the next set of strands avoiding the necessity of repositioning the mechanism to begin the process.
[0032] The foregoing and other features of the present invention will become more apparent from the following description and accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0033] [0033]FIG. 1 is a perspective view showing one version of the decorative curled ribbon after being processed;
[0034] [0034]FIG. 2 is a perspective view of the hand operated curl making machine of this invention;
[0035] [0035]FIG. 2A is a schematic view of the embodiment depicted in FIG. 2;
[0036] [0036]FIG. 3 is a view in perspective and schematic illustrating a portion of the automated machine of this invention;
[0037] [0037]FIG. 4 is a schematic illustration of the various stations on the drum and the actuation mechanisms associated with each of the stations for the automated machine of this invention;
[0038] [0038]FIG. 5 is an isometric exploded view illustrating the details of the curling mechanism of this invention;
[0039] [0039]FIG. 6 is a side view and schematic illustration of the curling mechanism of FIG. 5 illustrating the exit angle that the ribbon makes relative to the curling mechanism that can be changed to change the curling characteristic of the ribbon;
[0040] [0040]FIG. 7 is a partial view in perspective illustrating the clamping and cutting stations of this invention.
[0041] [0041]FIG. 8 a is a schematic illustration of the various stations on the drum and the actuation mechanisms associated with each of the stations for the automated machine of this invention where the drum is at a given location for one of the functions of the cycle;
[0042] [0042]FIG. 8 b is a elevated view of the a portion of the drum at one of the stations illustrating the position of the clamp and ribbons at the location of FIG. 8 a;
[0043] [0043]FIG. 9 a is identical to FIG. 8 a illustrating a different location of the drum at a different function of the machine during the cycle of operation;
[0044] [0044]FIG. 9 b is identical to FIG. 8 b illustrating the a different position of the clamp and ribbon at the location of FIG. 9 a;
[0045] [0045]FIG. 10 a is identical to FIG. 9 a illustrating a different location of the drum at a different function of the machine during the cycle of operation;
[0046] [0046]FIG. 10 b is identical to FIG. 9 b illustrating the a different position of the clamp and ribbon at the location of FIG. 9 a;
[0047] [0047]FIG. 11 a is identical to FIG. 10 a illustrating a different location of the drum at a different function of the machine during the cycle of operation;
[0048] [0048]FIG. 11 b is identical to FIG. 10 b illustrating the a different position of the clamp and ribbon at the location of FIG. 10 a;
[0049] [0049]FIG. 12 a is a partial view partly in section, partly in elevation and partly in schematic illustrating the anvil and stapling mechanism of this invention in the deployed position;
[0050] [0050]FIG. 12 b is identical view of FIG. 12 a illustrating the staple and anvil in the non-deployed position;
[0051] [0051]FIG. 13 is a plan view of the card feeding mechanism of this invention;
[0052] [0052]FIG. 14 is a block diagram showing the various actuators within the drum and the medium for actuating these actuators; and
[0053] [0053]FIG. 15 is a block diagram showing the various actuators outside of the drum and the medium for actuating these actuators.
[0054] These figures merely serve to further clarify and illustrate the present invention and are not intended to limit the scope thereof.
DETAILED DESCRIPTION OF THE INVENTION
[0055] While the invention in its preferred embodiment utilizes a particularized curling mechanism and stapling card it is be understood as one skilled in this art will recognize that this invention contemplates utilizing any type of curling mechanism and the stapling can be to any object such as a bow and the stapling can include other means of attaching the ribbons together and/or attaching objects thereto such as by fusion or adhesives or pinning or card locking or the like. It is also to be understood that the shape and/or configuration of the drum can take any form so long as it rotates about an axis and is capable of supporting the ribbons around the periphery thereof. As one skilled in this art will appreciate, the length of the strands are determined by the circumference of the drum and obviously, the length of each strand will be predicated on the circumference selected for the drum. For example a drum whose circumference is 38 inches (approximately 12 inches in diameter) will produce a curled ribbon that is 38 inches long and hence each strand will be 19 inches long.
[0056] The invention with respect to the hand operated embodiment can best be understood by referring to FIGS. 2 and 3. The portable hand operated curling machine generally illustrated by reference numeral 10 comprises the generally flat base 12 supporting a plurality of upstanding stub shafts or spindles 14 for supporting spools of ribbons 16 . In this instance, three spools of uncurled ribbons are shown, but it is to be understood that any number of spools can be utilized and the number of ribbons selected to form the curled ribbon end product is a matter of choice of the user. A complementary guide spool 18 for each of the spindles 14 are disposed between the curling mechanism 20 that is affixed to the base and the curling drum 26 for guiding the ribbon through the respective curling mechanism 20 . The curling mechanism will be described in detail hereinbelow. Each of the guide spools 18 are loosely fitted on a support spindle 22 affixed to base 12 . These guide spools 18 are free to rotate and afford substantially little if any resistance to the ribbon as is travels through the machine 10 . Another single guide spool 24 similarly attached to a support spindle affixed to base 12 and also loosely fitted to freely rotate is mounted between the curling mechanism 20 and the curling drum 26 and guides the three (3) ribbons in an overlapping configuration.
[0057] The curling drum 26 is rotatably supported to a stub shaft 28 affixed to base 12 and rotates thereabout by virtue of the movement of the handle 30 . Essentially the curling drum 26 consists of at least three stations, namely, the attachment or clamping station 32 , the cutting station 34 , and the stapling station 36 . The attachment station 32 , the cutting station 34 and the stapling station 36 are slots or holes and slots that extend through the width of the drum 26 or at least a sufficient distance to perform the functions as will be described immediately below and are formed adjacent the periphery of the drum 26 . The distance between the cutting station 34 and the stapling station 36 determines at which point the ribbons will be attached to each other. As shown in this embodiment the curled ribbons are being attached at their respective ends. To attach the ribbons at another point, for example, the cutting slot is formed at cutting station 34 a . At this station the ribbon will be attached intermediate the ends and will form a decorative curled ribbon as shown in FIG. 1.
[0058] In operation, each of the uncurled ribbons 16 are threaded and clamped through the respective curling mechanism, then laid adjacent to the respective guide spools 18 and then laid adjacent to the single guide spool 24 and the ends of the ribbons are held together in the overlapping position by the commercially available alligator clamp 38 which, in turn, is inserted by the operator into the aperture formed in the drum at the attachment station 32 . This secures the ribbons to the drum 26 . The operator with the use of the knob 40 affixed to handle 30 , rotates the drum 26 a number of revolutions until the desired end product is achieved, i.e. the number of curled ribbons constituting the end product is obtained. For example, if two (2) revolutions of the drum are made with three uncurled ribbons and the cut is 180° away from the staple station, the end product will include twelve (12) strands of curled ribbon emanating from the staple. On the other hand, if the cut is adjacent to the staple station, the number of strands of curled ribbons will be six (6), albeit twice as long. With an ordinary, commercially available stapler (not shown) with the base fitted into the slot 36 and the hammer head of the stapler straddling the ribbon, the staple is inserted into the ribbons. The stapling station 36 may include a wedged shaped portion 37 on either side of the slot which is designed to hold a card adjacent to the curled ribbons and in this instance the card is concomitantly stapled to the ribbons as shown in FIG. 1. The operator next, with the use of commercially available scissors (not shown) inserts the blades of the scissors to straddle the ribbons and snips the ribbons to produce the end item. Obviously, the ribbons can be cut with any other well known device, such as a knife or razor. The curled ribbons as processed by this portable curling machine produces the decorative piece as the end item which is ready for use to decorate a package, basket and the like. Obviously, from the foregoing it is easy to understand that the machine is so simple to operate that it is usable by practically all persons, is portable and sufficiently small and light weight to be easily stored.
[0059] The next portion of this application will describe the automated curling machine generally indicated by reference numeral 50 . Like the drum described in connection with the hand operated curling machine depicted in FIG. 2, this automated machine 50 also includes a drum that wraps the ribbon around the periphery thereof and the drum includes stations for clamping the ribbon, stapling and cutting the ribbons as will be described hereinbelow. Before describing the entire machine, it is noted that the curling mechanism shown in FIGS. 5 and 6 is substantially the same as the curling mechanism utilized in connection with the machine depicted in FIG. 2 and for the sake of convenience and simplicity this curling mechanism is being described at this point in the disclosure.
[0060] In its preferred embodiment the curling mechanism generally indicated by reference numeral 52 generally consists of two (2) generally cooperative flat plate elements 54 and 56 . Obviously, any type of mechanism that imparts a frictional force when the ribbon is moved in contact therewith that produces a curl can be employed. This particular mechanism has been selected because the exit angle can be changed so as to control the degree of curl in the ribbon as will be explained in more detail hereinbelow. The plate 54 may include a dowel pin 58 that fits into the drilled hole 60 to prevent the plate from rotating and a bolt 62 that fits through hole 64 formed in plate 56 and is threaded to the complementary threads 66 formed in the bore 68 to support the plates together leaving a small gap for allowing the ribbon to pass therebetween. The leading edge 70 of plate 54 is rounded to minimize the friction between that edge and the ribbon passing thereover and the portion 72 adjacent the bottom edge of the plate 56 is recessed and beveled to define a blade-like element where the ribbon comes into contact therewith as it is drawn thereover. A like configuration is provided on the diametrically opposed side to allow either side of the plate 56 to be used.
[0061] As shown in FIG. 6 the ribbon as depicted by the arrow A is threaded over the curved surface of plate 54 and passes between plates 54 and 56 and then over the edge 74 of the recessed portion 72 and led away therefrom as indicated by arrow B. In these embodiments there is virtually no tension in the ribbon upstream of the curling mechanism 52 , save for the amount needed to allow the ribbon to progress through the machine and most of the tension on the ribbon occurs between the edge 76 and the drum. By virtue of this arrangement, the curling mechanism 52 can be oriented to change the angle C formed between the plate 56 and the ribbon. The angle C that is selected will determine the curvature of the curl in the ribbon. In other words, a more acute angle will impart a more severe curl and a less acute angle, i.e. an angle closer to 90 degrees will impart a larger diameter curl.
[0062] In addition to the curling mechanism, as described above, the automated machine as best seen in FIG. 3 includes the rotating drum 80 with specific stations (similar to those depicted in FIG. 2), namely, the ribbon clamping station 82 , the cutting station 84 and the stapling station 86 . The ribbons are similar to FIG. 2 mounted on the base 86 and includes a slotted upstanding member 81 that guides each of the ribbons into the curling mechanism 52 , the guiding spools 83 and 85 also similar to that shown in FIG. 2. The base 88 supporting the drum 80 for rotary motion is supported in an upright position by a suitable cabinet 90 so that when the end product is completed it will fall by gravity to the bottom. The card feeding mechanism 92 which is sequentially placed in position at the stapling station may be pivotally mounted to swing radially outward away from drum 80 after the stapling so that after being cut in the cutting station 92 it will avoid being snag or tangled with the machinery.
[0063] The actuators for controlling the function at the various stations of the drum during operation of the machine are supported internally of the drum in this embodiment and the actuators for controlling the card feeding and card cutting mechanisms are located away from the central portion of the drum and will be described in detail hereinbelow. A control panel generally illustrated by reference numeral 93 mounted on the machine includes suitable commercially available switches that serve to turn on and off the machine, to override the automatic sequence of the machine's functions which are controlled by a central processing unit 94 , that sequences the rotation of the drum, controls the various actuators both internal and external of the drum and the electric motor 96 , as will be explained hereinbelow. The main control for the machine is a special digital computer including a programmable logic controller unit (PLC) that serves to control the sequencing operations of the machine. The control panel may contain control buttons for jogging the rotational position of the drum, permitting individual actuation of the actuators so as to allow the initial threading of the ribbons, to initiate the automatic and continuous operation of the machine and may include an emergency stop. The PLC is commercially available, as for example, from the Mitsubishi Company of Japan and is of the type that can be programmed which is typically done by a computer programmer to perform the necessary functions as needed.
[0064] [0064]FIGS. 4, 7 a , 7 b , 8 a , 8 b , 9 a , 9 b , 10 a and 10 b , illustrate schematically the details of the machine excluding the card feed and card cutting mechanisms. As noted therein the drum 80 at the clamping station 100 and cutting station 102 is flattened and this flattened portion 103 has disposed adjacent thereto the jaws 104 and 106 and the cutting blade 109 . Actuators 108 , 110 , 112 and 114 serve to control the position of jaws 104 and 106 . Actuator 108 serves to rotate jaw 104 , actuator 110 serves to rotate jaw 104 , actuator 112 serves to position jaw 104 radially outwardly relative to jaw 106 and actuator 114 serves to position both jaws 104 and 106 radially outwardly together with respect to the drum 80 .
[0065] This portion of the description will describe the operation of the clamping mechanism and referring next to FIG. 7, the flattened portion 103 at clamping station 82 includes a recess portion 120 for receiving the jaws 104 and 106 and the partially annular groove 122 partially extending around the circumference receives and guides the first layer of the six (6) curled ribbons. As noted the jaws are in the clamped position in this FIG. 7. In the initial threading of the machine and before clamping this layer of curled ribbons between the jaws 104 and 106 , these jaws are positioned radially outwardly relative to drum 80 and jaw 104 is positioned radially outwardly with respect to jaw 106 providing a gap to accept the curled ribbons (noting that in this embodiment that each layer includes six (6) curled ribbons). Once the clamp is threaded, the jaws are brought together and retracted into the recess portion 120 to clamp the ribbons, and the initial layer of ribbons rides in groove 122 by virtue of ac the electric servo motor 96 to rotate drum 80 . After the drum has rotated one or more revolutions depending on the number of strands that are required to make up the desired end product the clamping mechanism will be activated to release the layers of ribbons constituting the end product and re-activated to capture the layer of ribbons for the next cycle of operation so as to mass produce the end product. For example and for explanation purposes, assume that the end product will contain twenty-four (24) strands of curled ribbons emanating from the staple, noting that the cutting of the ribbon is 180° away from the stapling station, the drum will make two revolutions (each revolution of the layer of six (6) ribbons makes 12 strands relative to the staple). After the first revolution and when the second bundle of six curled ribbons overlay a portion of the first bundle of six curled ribbons, the combined underlayer and over layer will hold the ribbons to the drum without the assistance of the clamping mechanism. This portion of the machine's operation is shown in FIGS. 8 a and 8 b where it can be seen that the underlayer is clamped between the jaws and the over layer lies over the jaws.
[0066] At this juncture point of the machine operation the jaws are actuated to perform a sequence of moves so as to clamp the next layer of six (6) ribbons to be ready for the next cycle. One cycle produces one end product. While the drum is rotating the cylinders 112 , 108 and 110 are actuated to open the jaws and rotate the jaws downwardly below the ribbon path. This permits the jaws to release the underlayer of ribbons and to be moved away from the path of the ribbons drawn over the drum 80 . Cylinder 114 is then actuated to position the jaws 104 and 106 away from the drum. This is demonstrated in FIGS. 9 a and 9 b.
[0067] Before the completed revolution of the second layer of ribbons and during the first cycle, the lower jaw 104 is rotated back in the path of the ribbon by cylinder 110 as seen in FIGS. 10 a and 10 b . After the portion of the second layer of ribbons passes over the lower jaw 104 the cylinder 108 is actuated to bring the upper jaw 106 in line with the lower jaw 104 and the cylinder 112 is activated to bring both jaws together and clamp the ribbon as seen in FIGS. 11 a and 11 b . The jaws 104 and 106 are held radially outwardly away from drum 80 until after the cutting and stapling occurs and the next cycle commences.
[0068] This portion of the description describes the cutting and stapling operation of the automatic curled ribbon making machine. After the clamp secures the bundle of ribbons to begin the next cycle, the motor is activated to the stop position. While it isn't necessary to stop the rotation of the drum since it is possible to perform the next operations while the drum is moving, in its preferred embodiment the stapling and cutting is done while the machine is at rest. To perform the cutting operation, cylinder 140 is actuated to rotate the blade 142 extending through an aperture 144 formed in drum 80 . Blade 142 is pivotally connected to drum 80 by the pin 146 and the reciprocating action of the connecting arm pivots the blade 142 to cause it to cut through the ribbon.
[0069] Obviously, it is necessary to staple or join the respective layers of six ribbons prior to the cutting operation and this portion of the description describes the stapling operation of the machine. The stapling is accomplished in the preferred embodiment by a commercially available industrial type of cartridge feed stapler 146 which may be a Swingline stapler obtained from Swingline Inc. of Long Island City, N.Y. As best seen in FIGS. 12 a and 12 b the stapling is done at the stapling station 86 which similar to the cutting and clamping stations is a flattened portion 152 of the periphery of drum 80 . Stapler 146 includes a hammer 154 actuated by cylinder 156 that urges the continuous feed staple 158 toward the anvil 160 that causes one of the staples to pass through the ribbon and card 162 to secure all the individual ribbons and card together to form the end product. The raising and lowering of the anvil 160 is controlled by the cylinder 166 that pushes the pivoted links 188 and 200 via push rod 204 to cause the Y-shape to an I-shape to drive the anvil block 202 up and down.
[0070] The automatic card feeder 220 as best shown in FIG. 13 serves to automatically feed the cards 222 between the anvil 160 and staple 154 (FIGS. 12 a and 12 b ). The cartridge of cards is feed to the feeder 220 and the cards are urged toward the anvil 160 via the actuator 224 until properly located. The commercially available rotary cutter 226 and cylinder 228 serve cut the card after being stapled to the ribbons. The automatic card feeder 220 is mounted to the base 88 (FIG. 3) adjacent to the drum 80 by the actuator 230 and push rod 232 which supports the automatic card feeder 220 for pivotal movement away from drum 80 once the card is attached to the ribbon and held by the automatic card feeder 220 . Once the end product is spaced away from the drum 80 the card is cut and released from the card feeder 220 and allowed to drop into a suitable carton or conveyor belt as the case may be. If necessary, a blow off nozzle or as many as need be may be employed to assure that the strands of ribbons, which are essentially free floating from the card, does not become ensnared with the mechanism.
[0071] To understand the medium for controlling the various function of the automated curled ribbon curling machine and the interconnection between the various components reference will now be made to block diagram configuration of FIG. 14. In this diagram all of the solid lines represent electrical connection, all of the dash lines represent pressurized air feed hoses connections and all of the dot/dash lines represent feedback connections to the PLC. The PLC produces sequential signals to the individual commercially available solenoid valves generally indicated by reverence numeral 240 . Each cylinder is connected to the air manifold which is connected to a supply of pressurized air by virtue of opening and closing the respective solenoid valves to actuate and de-actuate the respective cylinder. Cylinder 108 actuating jaw 104 , cylinder 110 actuating jaw 106 , cylinder 140 actuating the cutter 142 and cylinder 166 actuating the anvil 160 are commercially available compressed air actuated actuators and suitable actuators of this type, for example are Clippard Cylinders available from the Clippard Instrument Laboratory, Inc. Of Cincinnati, Ohio. The cylinder 156 actuating the stapler and the cylinder 112 actuating the jaws to cause them to separate are also commercially available compressed air actuator and a suitable actuator is a Festo pneumatic actuator available from the Festo Inc. Of Hauppauge, N.Y. The cylinder 114 actuating both jaws together is also a compressed air actuator and a suitable actuator is a Fabco-Air available from Fabco-Air of Gainesville, Fla. The card feed actuator cylinder 224 and the rotary cutter cylinder 228 are also commercially available and a suitable actuator is a Bimba, available from Bimba Manufacturing Company, Monee, Ill.
[0072] It is apparent from the foregoing that the PLC will generate sequential signals to cause the various solenoid valves 250 , 252 , 254 , 256 , 258 , 260 , 262 and 264 to interconnect or disconnect the compressed air from a suitable source 290 to feed each of the cylinders through the respective hoses 270 , 272 , 274 , 276 , 278 , 280 , 282 and 284 to perform the functions as was described in the above paragraphs. The blowoff nozzle 292 is shown and as noted above is utilized to assure that the end product doesn't become ensnared with the operating mechanism of the curled ribbon machine and is only used as needed. Feed back sensors for the cutter 142 , stapler 146 and anvil 160 serve to feed back the position of each cylinder to the PLC via the lines 294 , 296 and 298 .
[0073] [0073]FIG. 15 is a block diagram similar to FIG. 14 but showing the functions that are not on the drum namely, the card feed cylinder 224 , the swing arm cylinder 230 , and the card cutter cylinder 226 . The solenoid valves 310 , 312 and 314 are controlled by the PLC and serve to connect the compressed air to the cylinders 224 , 230 and 226 via the air hoses 316 , 318 and 320 , respectively, for providing the respective functions. Feedback for the positions of these respective cylinders are fed back to the PLC through lines 322 , 324 and 326 , respectively. The PLC likewise controls the on/off and position of the motor via the motor driver 338 and encoder 340 . Each of the ribbons are provided with a break sensor 300 that is connected to the PLC via the feed back line 302 .
[0074] What has been shown by this invention is different embodiments of a machine for making curled ribbon products, say a multicolored multiple ribbons formed into a plurality of strands of curled ribbon, either individually or by mass production. The individual making is by a portable hand operated machine that includes a drum or reel for winding the ribbon and drawing it through a curling mechanism, where the drum includes stations for attaching the ribbons to the drum, stapling the ribbons and a card or other item together, and cutting the ribbons to form the desired end product. In the mass production machine, the stations are formed on the periphery of the drum and the attaching is by a judiciously sequenced clamping mechanism and a automatic stapling mechanism that accepts cards from an automatic card feeding mechanism so as to staple the ribbons and card together and discretely positioned the end product away from the drum when releasing the end product from the machine.
[0075] Although this invention has been shown and described with respect to detailed embodiments thereof, it will be appreciated and understood by those skilled in the art that various changes in form and detail thereof may be made without departing from the spirit and scope of the claimed invention. | In one embodiment a hand operated machine for making curly ribbon products comprises a rotary drum that includes a station to attach the uncurled ribbons (more than one), a cutting station to cut the curled ribbons, and a stapling station to staple the ribbons together or to a card, ribbon, or the like. A handle is provided to rotate the drum and a fixed curling mechanism mounted downstream of the drum serves to curl the ribbon as the drum rotates to place the ribbon in contact with the curling mechanism. In another embodiment the machine is automated and includes a drum that has the same stations. The attaching station includes a pair of jaws that are sequentially movable one relative to the other and together to attain attaching the ribbons to the drum for the first cycle, detaching the ribbon during the first cycle and attaching the succeeding ribbon used in the next cycle for mass producing the curly ribbon product. The stapling and cutting are automatic and the card feeding machine is movable relative to the drum to avoid snarling the ribbon when released. The curling mechanism is adjustable to change the exit angle to select the desired curl characteristics of the curled ribbon. | 3 |
BACKGROUND OF THE INVENTION
The present invention relates to marine propulsion assemblies. More specifically, the present invention relates to marine drive units having a skeg element that precedes a propeller for steering control, propeller protection and running stability.
Traditionally, outboard and stern marine drives have included a vertical drive shaft surrounded by and aligned within a faired housing that is secured to a vessel transom. The lower end of the drive shaft housing is terminated by a gear case or pinion housing. A propeller mounting arbor is aligned within the gear case and projects from the aft end of the case. The internal end of the arbor carries a pinion gear that meshes with a corresponding drive shaft pinion thereby turning the rotational drive line 90°.
Outside of a gear case end wall seal, the projected end of the arbor shaft receives the marine drive propeller by such structural devices as will transmit torque and rotating power to the propeller with accommodation for some degree of shock absorption.
Below the gear case and, traditionally, as an integrally cast extension therefrom, is a radially projecting skeg element. Classically, a skeg is an extended vessel keel that is constructed and positioned to protect the lower rotational arc of a propeller or screw from engaging the bottom of the floatation water body or any submerged obstacles. In an outboard or stern drive, the skeg performs a similar propeller protection function but also functions as a steering rudder. In higher speed ranges, the skeg becomes increasingly important to lateral stability of the vessel and for propeller counter-torque trim.
When a propeller driven light utility or racing vessel achieves speeds in excess of 75 miles per hour, for example, the vessel hull is supported, in large measure, aerodynamically. The only vessel contact with the water support surface is an extremely small area planing pad at the vessel transom.
For running at speeds in this realm, a vessel is preferably "trimmed" to set the propeller thrust axis in the plane of the vessel planing pad. As a direct consequence, half or less than half of the propeller rotational circle is submerged. The skeg, which is leading the propeller through the water, is therefore essential for lateral stability as well as propeller counter-torque and directional control. Directional control also includes opposition to propeller induced yaw moments. The trailing edge of the skeg is given a small cant from planar alignment with the propeller thrust axis for production of a counter yaw-force.
Structural failure of the skeg at high speed can precipitate disastrous consequences. Consequently, the traditional industry manufacturing practice of integrally casting the skeg and lower gear case shell from weaker grades of casting aluminum that are selected more for a low casting temperature and a smoothly finished surface than for strength and toughness is disturbing to those who operate their equipment in these high speed realms.
From another perspective, at high planing speed the skeg profile area, projected into the propeller thrusting arc, represents a significant proportion of the emersed propeller arc. The degree of such proportion is enlarged by the greater skeg sectional thickness required as a consequence of inherently weak fabrication materials. Hence, the magnitude of power robbing drag imposed by the skeg frontal section area is exponentially amplified due to weak fabrication materials.
Furthermore, this skeg profile projection greatly reduces the propeller drive efficiency over the propeller rotational arc past the skeg projection. In brief, the prior art methods of skeg construction disturbs the water ahead of the propeller arc. At these speeds, the result of this disturbance is a turbulent wake behind the skeg. When the propeller blade engages the turbulently disturbed increment of water behind the skeg, thrust efficiency declines.
In other words, the turbulent slip stream left behind the skeg carries a wake of microeddys and counterflows that were generated and energized by passing around the skeg surface. When the propeller blade engages this wake stream, a certain portion of the fluid in that wake has been thrust into directions of high energy movement contrary to the propeller blade pitch bias. Consequently, the acceleration vectors of the propeller activated fluid mass are directionally dispersed thereby reducing the reaction forces along the propeller thrust axis.
Additionally, this turbulent disturbance of the propeller thrust efficiency occurs at the most inopportune position in the semicircular propeller thrust arc. Vertically beneath the gear case, the propeller rotational arc has just attained maximum efficiency by cutting into undisturbed water with a fully wetted blade. At the water surface, the blade enters the liquid body from a gaseous body (atmosphere) thereby carrying a compressible gas surface coating on the blade into the incompressible fluid mass. As the gas is purged from the blade proximity and surface by water displacement, some slippage occurs to diminish the propeller efficiency over that increment of the already reduced proportion arc. Beyond the surface disturbance arc but before the skeg wake, the propeller blade reaches maximum thrust efficiency. When the propeller blade enters the skeg wake, this maximum thrust is instantly compromised and reduced. After passing the skeg wake, the propeller blade no sooner sheds the skeg induced microturbulence than advance elements of the propeller blade root start to rotationally rise out of the undisturbed water.
With respect to a more subtle function of a high speed, outboard drive unit skeg, the dynamics of a particular submerged propeller arc are that the propeller produces more propulsive thrust on one side of the propeller axis than on the other. This asymmetric thrust necessarily induces a yaw moment. Untrimmed, propeller induced yaw moment must be corrected by a cant in the propulsion axis to the direction of travel. This cant in the propeller thrust axis induces additional drag, power consumption and reduced speed. More efficiently, propeller induced yaw is corrected by a slight steerage curl in the vertical trailing edge of the skeg. The direction of the steerage curl is determined by the propeller rotational direction. The degree of steerage curl for a particular equipment combination is somewhat more ambiguous. Moreover, counter yaw skeg curl adjustment by trial and error is frustrated by the fact that the cast aluminum fabrication materials have low properties of yield and ductility. Excess or repeated bending on the skeg structure results in a fracture. Hence yaw control curl must be cast into a cast aluminum skeg. Finding the optimum degree of yaw control curl for a particular combination of boat, engine and propeller can be a frustrating and expensive quest.
Another source of high speed wake turbulence from an outboard marine drive into the propeller arc surprisingly comes from the engine cooling water inlets. Traditionally, these inlets are one or more small apertures, 2 to 4 holes of about 1/4 in. diameter, for example, in the frontal surface of the drive unit gear case that channel pickup water into an engine cooling water supply pump. Forward velocity of the gear case drives water into the apertures and generates a substantial dynamic pressure head into the engine coolant pump suction port. Cooling water discharge from the pump is channeled into a pipe located internally of the drive shaft housing. Water from the pump discharge pipe is delivered to the engine cooling jackets.
Since these water inlets represent surface discontinuities on the gear case, water flowing past an inlet but not entering the inlet is directionally disrupted. This directional disruption consequently initiates a turbulent wake that follows the gear case surface into the propeller arc.
It is, therefore, an object of the present invention to position the skeg under the gear case at a location that maximizes the arc of maximum blade thrust efficiency.
Another object of the invention is to increase the area of undisturbed water available to the propeller.
Still another object of the invention is to reduce the skeg profile area.
A still further object of the invention is to provide a slimmer yet stronger skeg structure.
Another object of the invention is to provide a stronger skeg assembly with the gear case.
An additional object of the invention is to provide an easily detachable and replaceable skeg in the event of loss or damage.
Also an object of this present invention is a skeg construction that reduces the magnitude of skeg wake turbulence and drag.
Another object of the invention is removal of an engine cooling water inlet aperture to a less turbulence inducing position on the drive unit gear case.
Another object of the invention is to provide a convenient and flexible means for experimentation with the skeg trim parameters and to maximize the boat performance and efficiency.
SUMMARY OF THE INVENTION
These and other objects of the invention as will subsequently become apparent from the following detailed description, are accomplished by a gear case for an outboard or stern drive having an extremely thin, approximately 1/4 in. stainless steel skeg that is off-set from the central vertical plane through the propeller drive arbor axis. The skeg off-set direction is toward the propeller lifting quadrant portion of the submerged propeller semicircle. By asymmetrically aligning the skeg plane near a tangent to the gear case shell, more material area and volume may be engaged to increase the strength of the connective interface with the gear case without disproportionately increasing the parasitic drag area of the gear case.
Such additional joint area and volume permit a deep, T-section bayonet socket tangentially into the gear case shell wall to longitudinally receive a bayonet blade having an upper end T-head projecting from an integral connection with an extremely thin, high strength steel (preferably stainless steel) skeg. Alternatively, the gear case wall may be reinforced with integrally cast bosses to which a thin blade skeg may be secured with flush head machine screws.
Since stainless steel and other ductile, high strength metals may quickly and repeatedly be removed from an integral case boss, the process of finding and correcting the degree of yaw trim for a particular boat and engine combination is greatly facilitated. Yaw trim is further facilitated by the capacity of ductile metals to be relatively easily cold formed.
As a secondary utility, a laterally offset skeg mounting boss provides a nearly ideal envelope for engine cooling water scoops, which may be connected with a cooling water delivery pipe internally of the drive shaft housing.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 pictorially illustrates a typical prior art marine outboard propulsion unit;
FIG. 2 pictorially illustrates a typical lower drive unit as modified by the present invention;
FIG. 3 is a bottom plan view of the invention;
FIG. 4 is an axial end view of the invention;
FIG. 5 is a sectioned bottom view of the skeg trailing edge for trial and error correction of the propeller yaw;
FIG. 6 is an end elevational view of a first skeg assembly joint embodiment of the invention set in the traditional bottom center position;
FIG. 7 is an end elevational view of a second skeg assembly joint embodiment of the invention;
FIG. 8 is an end elevational view of a third skeg assembly joint embodiment of the invention;
FIG. 9 is an end elevational view of a fourth skeg assembly joint embodiment of the invention;
FIG. 10 is an end elevational view of a fifth skeg assembly joint embodiment of the invention;
FIG. 11 is a side elevational view of the fifth skeg assembly joint embodiment of the invention;
FIG. 12 is an end elevational view of a sixth assembly joint embodiment of the invention; and,
FIG. 13 is a side elevational view of the sixth assembly joint embodiment of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Relative to the drawings wherein like reference characters designate like or similar elements throughout the several figures of the drawings, FIGS. 1 and 2 illustrate an outboard boat propulsion unit comprising an engine 10 for rotatively driving a vertically disposed drive shaft enclosed within a drive shaft housing 12. The drive shaft is terminated at its lower end with a pinion or bevel gear that meshes with a corresponding pinion at the end of a propeller arbor 14 to turn the rotational axis of the drive line substantially 90° from vertical to horizontal.
A vertical axis steering post 15 is secured to a boat transom mounting bracket 16. The lower end 17 of the drive shaft housing supports an anti-cavitation plate 18 above a torpedo shaped gear case or pinion housing 20. A bearing seal 21 isolates the gear case interior from the surrounding water and a coaxial journal or antifriction bearing maintains the axial alignment of the propeller arbor 14 with the thrust axis 22. The drive propeller 13 is secured to the external end of the arbor shaft 14 by a calibrated shock absorption or shear mechanism such as a friction clutch, an elastomer sleeve or a shear pin.
The gear case 20 comprises a bulbus shell confining the interior end of the propeller arbor 14 and the meshing pinion gears. The prior art construction of FIG. 1 illustrates a center plane aligned skeg 26 projecting vertically downwardly from the gear case 20 in substantially co-planar alignment with the propeller drive shaft. Also prior art but illustrated as combined with the invention embodiments of FIGS. 2 and 3 are engine cooling water inlet slots 27. Although three slots 27 are shown, it will be understood to those knowledgeable of the art that more or less such inlet slots or holes may be positioned around the frontal surface area of the gear case 20; usually about the lower half of the case. Those slots 27 are apertures through the gear case shell that are fluid flow connected to the suction port of the engine coolant circulation pump not shown. Discharge from the pump is channeled into the pipe 25 that rises internally of the drive shaft housing 17 and into the engine cooling jackets.
Constructed according to the present invention as illustrated by FIGS. 2, 3 and 4, the skeg 30 is substantially planar and aligned generally parallel with the thrust axis 22 but laterally off-set therefrom. As best illustrated by FIG. 4, at high speed the boat planing pad 24 is riding the water surface thereby placing the thrust axis 22 of the propeller 13 substantially in or even slightly above the water surface plane 28. Consequently, less than half of the propeller circle is below the water surface. The dashed line semicircle 50 represents the blade sweep of the propeller 13. As viewed frontally from aft of the propeller toward the boat bow, the propeller rotational direction is usually clockwise. However, rotational direction is usually a matter of design convention and convenience. The present description is directed to a clockwise rotation. A cross-hatched area 52 is shown to be bounded between the semicircle 50 and gear case boss 34 and between the prior art skeg position 26 and the present invention skeg 30. This cross-hatched area 52 is laterally off-set to the side of the vertical plane 54 defined by the thrust axis 22. Such lateral displacement is in the direction of the upturning or third quadrant of the propeller circle. Since the down turning second quadrant of the propeller circle is the most efficient of the two, that greater efficiency is continued and enhanced by the invention taught hereby. Hence a significant speed increase may be obtained from a given drive system. Synergistically, the skeg drag may be further reduced by using a sharp, narrow, high tensile strength metal plate skeg. For example, 1/4" high nickel alloy or "stainless steel" plate with a highly polished surface provides a skeg of great strength and extremely low fluid resistance. Compared to prior art cast aluminum skeg designs, a thin stainless steel plate skeg may reduce the frontal, cross-sectional area of the skeg by half.
With continuing reference to FIG. 4, an enlarged sector of the gear case shell projects about 45° down into the third quadrant of the clockwise propeller rotation from the propeller thrust axis 22. This enlargement provides a boss 34 for supporting the skeg load. Within the boss 34 is an elongated channel 36, either machined or cast, that functions as a bayonet slide socket to receive the slide inserted T-head 38 of the skeg 30 into position. In its fully inserted position, the skeg is secured by pins or screws not shown. The FIG. 4 embodiment aligns the mounting T-head at about 45° from the plane of the skeg blade 30 to vertically orient the skeg plane.
The T-head 38 insert edge of the skeg 30 may be extended along the full length of the respective skeg mounting root thereby providing a relatively long and continuous load distribution area. If the skeg is formed of a high nickel alloy steel, the T-head sectional shape may be machined, forged or cast. As previously described, the T-head 38 mounting edge of the skeg is preferably inserted into the T slots 36 of the gear case boss 34 by a longitudinal sliding motion. Final longitudinal position may be secured by transverse fasteners such as pins or set screws. This assembly may also employ a shallow angle taper in the T-head 38 and T slot 36 length to provide a predetermined longitudinal abutment position for the skeg along the T slot length and a significant frictional resistance to unintended longitudinal extraction.
As shown by FIG. 4, the lower ramp 35 of the boss 34 provides a flat lifting surface to the gear case 20. Since flat, horizontal surfaces generate immense lifting forces on a light sport boat at speeds exceeding 100 m.p.h., this gear case lifting surface 35 may in some cases become the primary hydrodynamic support surface for the boat. In such an equipment combination, the engine assembly is lifted vertically up along the boat transom to align the plane of the lower ramp surface 35 near the boat planing pad 24. The boat bow weight is supported aerodynamically.
The invention embodiment of FIG. 6 illustrates a broader utility of the T-head bayonet mount 38 for a narrow plate stainless steel skeg 33 located in the prior art bottom center position relative to the plane of the propeller thrust line. However, in the FIG. 6 embodiment, the skeg support bow 37 acts as a V-bottom boat hull to knife the water with a graduated lifting surface. Wings 56 from the gear case 20 are provided to accelerate acquisition of the boat planing attitude. Upon reaching sufficient speed in the planing attitude, the wings 56 will rise above the water running surface. Concave lower surfaces of the wings 56 are provided to shed running spray from under the wings 56 as quickly as possible thereby reducing the wetted surface area of the gear case above the waterline.
FIG. 5 illustrates critical elements of the invention yaw trim feature. From the perspective of viewing plane 5--5 of FIG. 4, the skeg 30 is seen to have a trailing edge 31 that is feathered toward the propeller thrust axis, 22. This feathering provides a counter yaw vector that offsets yaw forces imposed by the propeller. Those with skill in the art will understand that a cold cast aluminum skeg cannot be reliably feathered or shaped after casting. Consequently a cast aluminum skeg must have the counter yaw trim cast into the material structure. This allows little latitude for optimization by experimentation. Although the T-head skeg mount of the present invention provides greater flexibility for experimentation with numerous cast aluminum skegs, each having a different degree of trim feather cast into the skeg plane, a single skeg of a more ductile material such as nickel steel may be progressively feathered until optimized without necessarily removing the skeg from the gear case. Conversely, the skeg 30 may be easily removed from the gear case 20; first, for a more controlled and accurate feather stressing and second, for an accurate measurement of the degree of feather.
The invention embodiment of FIG. 7 sets the T-slot boss 42 in a horizontal alignment plane to receive a skeg 40 mounting T-head 44 turned at 90° to the skeg plane. This FIG. 7 configuration of the invention raises the lower surfaces of the boss 42.
FIG. 8 illustrates an embodiment of the invention wherein the thin plate skeg 45 is given a 45° bend 46 along the top edge thereof. A cast boss 47 is predominantly along the upper half of the gear case 20. In this case, the skeg is counter bored to receive flush head screw fasteners such as counter sunk machine screws 48.
FIG. 9 illustrates a simplified version of the invention having a thin straight skeg blade 60 flush mounted by countersunk machine screws 62 onto a flat bottom case boss 64. This configuration of the invention has many functional characteristics of the flat bottom T-head mount of FIG. 4.
FIGS. 10 and 11 are respective views of the same embodiment wherein a thin flat plate skeg 70 is attached to the boss 74 by countersunk machine screws 72. Formed within the boss 74, is a U-shaped conduit 76 having a plurality of small diameter water capture apertures 78 along the lower surface. An upper leg 77 of the conduit has an opening 79 into the engine cooling water pipe 25. Water ramed into the apertures 78 is driven through the conduits 76 and 77 into the water pump for delivery into the engine/cooling water pipe 25.
FIGS. 12 and 13 also are respective views of the same embodiment wherein a thin, flat plate skeg 80 is secured by countersunk machine screws 82 to a mounting boss 84. In this case, the boss 84 is cast with an open face channel 86 having frontally open water capture scoops 88. The open face of the channel 86 is enclosed by skeg plate 80, but the scoop channels remain open. These scoops admit engine cooling water into the channel 86 and ultimately into the engine coolant supply pipe 25.
The foregoing description of the preferred embodiments of my invention have been presented for purposes of illustration and description. They are not intended to be exhaustive or to limit the invention to the precise forms described. Obvious modifications or variations are possible in light of the foregoing teachings. The embodiments were chosen and described to provide the best illustration of the principles of the invention and its practical application and to thereby enable one of ordinary skill in the art to utilize the invention in various embodiments and with various modifications as is suited to the particular use contemplated. All such modifications and variations are within the scope of the invention as determined by the appended claims when interpreted in accordance with breadth to which they are fairly, legally and equitably entitled. As my invention, therefore: | An outboard or stern marine drive assembly includes a skeg that is detachably secured to the lower gear case. The skeg plane is laterally off-set from the vertical plane that passes through the propeller thrust axis. One embodiment of the thin, high-strength steel skeg is secured by a "T" section along the top edge of the skeg to mesh longitudinally with a corresponding T slot in the gear case wall. In another embodiment, the skeg is flush mounted to a boss surface cast integrally with the shell wall of the gear case. | 1 |
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0001] Not Applicable.
THE NAMES OF THE PARTIES TO A JOINT RESEARCH AGREEMENT
[0002] Not Applicable.
INCORPORATION-BY-REFERENCE OF MATERIAL SUBMITTED ON A COMPACT DISC
[0003] Not Applicable.
BACKGROUND OF THE INVENTION
[0004] 1. Field of the Invention
[0005] The present invention relates to automated currency processing and, more specifically, to the automated detection of a transparent gap present between subsequent bank notes undergoing high-speed processing.
[0006] 2. Description of Related Art including information disclosed under 37 CFR 1.97 and 1.98
[0007] In an effort to combat the counterfeiting of bank notes and other machine-processable security documents, substrate manufactures continue to develop and incorporate new security features into their product. For example, in some instances, one or more transparent stripes may be incorporated into a bank note. Such transparent stripes may be placed at a leading edge of the bank note, the middle portion of the bank note or any other portion of the bank note.
[0008] Current bank note processing machines feature numerous detectors and sensors to determine various attributes of a bank note being processed. A stack of bank notes may be provided as an input to a bank note processing machine. The bank note processing machine may then direct the bank notes one at a time through a transport path. As the bank notes travel through the transport path one at a time, they interact with the various detectors and sensors. The information gathered by the various detectors and sensors may then be compiled and/or analyzed to determine various characteristics of each bank note such as, for example, denomination, whether the bank note is counterfeit, how damaged the bank note is, etc.
[0009] When analyzing bank notes using a bank note processing machine, it is important to be able to distinguish between different bank notes that are travelling through the transport path. Specifically, it is desirable to determine when one bank note has left a particular detector and/or sensor and another bank note has entered. Typically, a bank note processing machine uses an optical sensor to distinguish between different bank notes. Specifically, one or more optical sensors may be placed at different positions along the transport path.
[0010] A typical bank note is opaque. Accordingly, as each bank note travels through the portion of the transport path where the optical sensors is located, the optical sensor detects an opaque material. There is a gap between the different bank notes traveling along the transport path. As a result, the optical sensor detects a transparent region once a bank note has passed by and before the next bank note has arrived at the optical sensor. This transparent region between subsequent bank notes is referred to herein as the “transparent gap”. Accordingly, the detection of a transparent gap is used by a typical bank note processing machine to distinguish between the different bank notes travelling along the transport path. However, with the introduction of bank notes having one or more transparent stripes, this typical method leads to a false distinction between the different notes. Specifically, what appears to be a transparent region indicating the end of one bank note and the beginning of another may in fact be a transparent stripe within the same bank note.
[0011] Accordingly, a need exists for a detector that can differentiate a transparent stripe on a bank note from a transparent gap between subsequent bank notes along the transport path.
BRIEF SUMMARY OF THE INVENTION
[0012] The present invention relates to automated currency processing and, more specifically, to the automated detection of a transparent gap present between subsequent bank notes undergoing high-speed processing.
[0013] In one embodiment, the present disclosure is directed to a system for distinguishing between bank notes in a bank note processing machine comprising: a conveyance device for transporting a bank note along a transport path; a detector comprising an optical sensor and an ultrasonic sensor disposed at a desired location along the path; wherein the optical sensor identifies a transparent region at the desired location, and wherein the ultrasonic sensor determines if the transparent region corresponds to a transparent gap.
[0014] In accordance with another embodiment, the present disclosure is directed to a method for identifying a transparent gap between subsequent bank notes comprising: directing one or more bank notes along the transport path; positioning a detector having an optical sensor and an ultrasonic sensor along the transport path, wherein the detector monitors the transport path; identifying a transparent region using the optical sensor; and determining if the transparent region corresponds to at least one of a transparent stripe and a transparent gap using the ultrasonic sensor.
[0015] In certain embodiments, the present disclosure is directed to an information handling system having machine-readable instructions to: direct one or more bank notes along the transport path; position a detector having an optical sensor and an ultrasonic sensor along the transport path, wherein the detector monitors the transport path; identify a transparent region using the optical sensor; and determine if the transparent region corresponds to at least one of a transparent stripe and a transparent gap using the ultrasonic sensor.
[0016] These and other improvements will become apparent when the following detailed disclosure is read in light of the supplied drawings. This summary is not intended to limit the scope of the invention to any particular described embodiment or feature. It is merely intended to briefly describe some of the key features to allow a reader to quickly ascertain the subject matter of this disclosure. The scope of the invention is defined solely by the claims when read in light of the detailed disclosure.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)
[0017] The present invention will be more fully understood by reference to the following detailed description of the preferred embodiments of the present invention when read in conjunction with the accompanying drawings, in which like reference numbers refer to like parts throughout the views, wherein:
[0018] FIG. 1A depicts a block diagram of a bank note processing machine in accordance with an illustrative embodiment of the present disclosure.
[0019] FIG. 1B depicts an illustrative bank note having transparent gaps.
[0020] FIGS. 2A-2C illustrate interaction of a detector with a bank note passing through a transport path; and
[0021] FIG. 3 depicts method steps for operation of a detector in accordance with an illustrative embodiment of the present disclosure.
[0022] The invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
DETAILED DESCRIPTION OF THE INVENTION
[0023] Typical currency processing machines comprise a bank note feeder device, a transport device or belt providing a transport path along which bank notes travel past several detectors, and a final disposition component, which may typically include a pocket for collection of processed bank notes, a strapper for strapping the bank notes in bundles, and a means for depositing the bank notes into the pocket by pulling the bank notes from the bank note processing path or transport device. As the bank note is processed, detectors along the transport path scan the bank note for various attributes. It is important to distinguish between the different bank notes passing along the transport path so that the characteristics of one bank note are not falsely attributed to another bank note.
[0024] FIG. 1A depicts a block diagram of a bank note processing machine according to an illustrative embodiment of the present disclosure, highlighting the location of the detectors with respect to the processing stream. In certain illustrative embodiments, a bank note is first stripped from a stack of notes in a feeder ( 102 ) and sent along a transport path ( 104 ) through a scanner module ( 106 ). Within the scanner module ( 106 ), one or more detector modules ( 108 ) may be disposed is an area centered on the transport path ( 104 ). As shown in FIG. 1A , the detector modules ( 108 ) are placed such that a bank note passing along the transport path ( 104 ) passes through the detector modules.
[0025] The detector modules ( 108 ) may be any suitable detector module known to those of ordinary skill in the art, having the benefit of the present disclosure. For instance, in certain implementations, the detector modules ( 108 ) may be used to detect the denomination of a bank note, whether the bank note is counterfeit, and/or perforations or other damage to the bank notes.
[0026] In accordance with an illustrative embodiment of the present disclosure, one or more detectors ( 110 ) may be disposed at different locations along the transport path ( 104 ). A detector ( 110 ) may be used to identify gaps between different bank notes that are transported along the transport path ( 104 ). Manner of operation of such detectors ( 110 ) is discussed in further detail below.
[0027] A detector ( 110 ) may be placed at any location along the transport path ( 104 ) where it is desirable to distinguish between different bank notes. For instance, in certain embodiments, a detector ( 110 ) may be placed before and/or after one or more of the detector modules ( 108 ). As a result, the detectors ( 110 ) may be used to determine when one bank note has exited a detector module ( 108 ) and another bank note has entered. This information may then be used to ensure that characteristics identified by each detector module ( 108 ) for a bank note passing therethrough are attributed to the correct bank note.
[0028] After passing through the detector modules ( 108 ) the information gathered by the detector modules ( 108 ) may be used to sort the bank notes. Specifically, certain bank notes (e.g., counterfeit notes) may go to a reject pocket ( 112 ). Further, some of the bank notes may be directed to an inline shredder ( 114 ) and destroyed. Other bank notes may be directed to a first stacker strapper inline bundler ( 116 ) and a second stacker strapper inline bundler ( 118 ). Finally, some of the bank notes may be directed to a run out pocket ( 120 ) positioned at the end of the transport path ( 104 ).
[0029] In certain implementations, a central processor (not shown) can be used to control and/or harmonize the operation of the various components of a bank note processing machine such as the one shown in FIG. 1A . The central processor may be an information handling system that is communicatively coupled to the bank note processing machine through a wired or wireless communication means. Operation of such communication means is well known to those of ordinary skill in the art and will therefore, not be discussed in detail herein.
[0030] An information handling system generally processes, compiles, stores, and/or communicates information or data for business, personal, or other purposes thereby allowing users to take advantage of the value of the information. Because technology and information handling needs and requirements vary between different users or applications, information handling systems may vary with respect to the type of information handled; the methods for handling the information; the methods for processing, storing or communicating the information; the amount of information processed, stored, or communicated; and the speed and efficiency with which the information is processed, stored, or communicated. The variations in information handling systems allow for information handling systems to be general or configured for a specific user or specific use such as financial transaction processing, airline reservations, enterprise data storage, or global communications. In addition, information handling systems may include or comprise a variety of hardware and software components that may be configured to process, store, and communicate information and may include one or more computer systems, data storage systems, and networking systems.
[0031] The central processor can be controlled by one or multiple computer processing devices, which control the timing of the system as well as activation of the detectors and control of bank note disposition. One of ordinary skill will appreciate that the central processor may be either a single processing unit or it may consist of multiple processors. Regardless of the configuration, the central processor performs the same function. Computer memory is also present, providing storage capacity for the computer code which controls the central processor's actions. The central processor is capable of running the stored program steps from the accessible memory. The processing device may be a dedicated general purpose computer, an embedded RISC or CISC computer processor, a DSP, or the like.
[0032] The details of operation of a detector ( 110 ) in accordance with illustrative embodiments of the present disclosure will now be discussed in conjunction with FIGS. 2A-C and the flow chart of FIG. 3 .
[0033] A detector ( 110 ) in accordance with illustrative embodiments of the present disclosure may be comprised of an optical sensor and an ultrasonic sensor. In certain embodiments, the optical sensor and the ultrasonic sensor of the detector ( 110 ) may be distinct components. In contrast, in certain embodiments, an integrated sensor which is operable as an optical sensor and as an ultrasonic sensor may be used as the detector ( 110 ).
[0034] FIG. 1B depicts an illustrative bank note 10 that may be processed using the methods and systems disclosed herein. As shown in the figure, the bank note 10 may include one or more transparent gaps 12 . The bank note of FIG. 1B is shown for illustrative purposes. Accordingly, the transparent gaps 12 may be oriented as desired for a particular note without departing from the scope of the present disclosure.
[0035] FIG. 2A depicts a bank note ( 202 ) passing along a transport path ( 104 ) having a detector ( 110 ). The detector ( 110 ) includes a transmitter ( 110 A) and a receiver ( 110 B) disposed along the transparent path ( 104 ) such that any bank note travelling along the transport path ( 104 ) would pass through between the transmitter ( 110 A) and the receiver ( 110 B). In the illustrative embodiment of FIG. 1 , the transmitter ( 110 A) and the receiver ( 110 B) are disposed on opposing sides of the transport path ( 104 ). The specific orientation of the transmitter ( 110 A) and the receiver ( 110 B) is shown for illustrative purposes only. Accordingly, the transmitter ( 110 A) and receiver ( 110 B) may be oriented differently without departing from the scope of the present disclosure. As shown in FIG. 2A , while the bank note is passing along the portion of the transport path ( 104 ) corresponding to the detector ( 110 ), the optical signal ( 204 ) transmitted by the transmitter ( 110 A) is impeded by the bank note. As a result, the optical signal received by the receiver ( 110 B) will be below a pre-set threshold value indicating that the optical path between the transmitter ( 110 A) and the receiver ( 110 B) is blocked. Accordingly, the optical sensor of the detector ( 110 ) detects an opaque region corresponding to the bank note ( 202 ).
[0036] As shown in FIG. 2B , once the bank note ( 202 ) passes by the detector ( 110 ), the optical signal ( 204 ) transmitted by the transmitter ( 110 A) is no longer impeded by the bank note ( 202 ) and will be received by the receiver ( 110 B). Accordingly, the optical sensor of the detector ( 110 ) will detect a transparent region. Once a transparent region is detected by the optical sensor of the detector ( 110 ), the ultrasonic detector of the detector ( 110 ) is activated and transmits an ultrasonic signal ( 206 ). If the transparent region identified by the optical signal ( 204 ) corresponds to a transparent stripe in the bank note ( 202 ), the ultrasonic signal ( 206 ) is impeded by the transparent region of the bank note ( 202 ). Accordingly, the ultrasonic signal ( 206 ) received by the receiver ( 110 B) will be below a pre-set threshold value indicating that the path between the transmitted ( 110 A) and the receiver ( 110 B) is blocked by a bank note. In contrast, if as shown in FIG. 2C , the transparent region corresponds to a transparent gap between subsequent bank notes, the ultrasonic signal ( 206 ) will not be impeded by the bank note and the signal received at the receiver ( 110 B) will be above a pre-set threshold value indicating the existence of a transparent gap.
[0037] As would be appreciated by those of ordinary skill in the art, having the benefit of the present disclosure, any suitable optical sensor or ultrasonic sensor may be used in the detector ( 110 ) without departing from the scope of the present disclosure.
[0038] Turning now to FIG. 3 , method steps for analyzing bank notes directed through a bank note processing machine in accordance with an illustrative embodiment of the present disclosure are depicted. As shown in FIG. 3 , first, at step 302 , the optical sensor of the detector ( 110 ) is monitored. In certain embodiments, a central processor as discussed above may monitor and manage the operation of the detector ( 110 ). For instance, the central processor may manage transmission of optical and/or ultrasonic signals by the transmitter ( 110 A) and monitor the signal received by corresponding receivers.
[0039] Next, at step 304 it is determined whether the optical sensor is detecting an opaque region or a transparent region. In certain implementations, an opaque region is detected if the optical signal received by the receiver ( 110 B) is below a pre-set threshold value and a transparent gap is detected if the optical signal received by the receiver ( 110 B) is above a pre-set threshold value. Detection of an opaque region is indicative of the fact that a bank note is passing along the transport path through the region corresponding to the detector ( 110 ). Accordingly, the process returns to step 302 to monitor the optical sensor. This cycle continues until it is determined at step 304 that the optical sensor is detecting a transparent region (i.e., it is not detecting an opaque region).
[0040] If a transparent region is detected at step 304 , the process continues to step 306 and the ultrasonic detector of the detector ( 110 ) is activated. At step 308 it is determined whether the ultrasonic signal received by the receiver ( 110 B) is above a pre-set threshold value. Specifically, if the transparent region detected by the optical sensor of the detector ( 110 ) corresponds to a transparent stripe and not a transparent gap, the transparent stripe impedes the transmission of ultrasonic signals generated by the transmitter ( 110 A). As a result, the ultrasonic signal received by the receiver ( 110 B) will be below a pre-set threshold value. It is thus concluded that the transparent region corresponds to a transparent stripe in a bank note and the process is returned to step 302 to continue to monitor for the next occurrence of a transparent region.
[0041] In contrast, if the ultrasonic signal is transmitted through a transparent gap, it is not impeded. As a result, the ultrasonic signal received by the receiver ( 110 B) will be above a pre-set threshold value indicating that the transparent region is in fact a transparent gap. Accordingly, if the ultrasonic signal received at the receiver ( 110 B) is above the pre-set threshold value, the process continues to step 310 and it is concluded that the transparent region is a transparent gap between subsequent bank notes. Next, at step 312 , the optical sensor of the detector ( 110 ) continues to monitor the transport path ( 104 ) until an opaque region is detected indicating arrival of another bank note. The process is then reset at step 314 and returned to step 302 . The above steps are then repeated to determine when the new bank note has passed through the detector ( 110 ).
[0042] As would be appreciated by those of ordinary skill in the art, having the benefit of the present disclosure, while the present embodiment depicts use of a single optical detection device and a single ultrasonic detection device, other embodiments may use multiple instances of each. Further, as would be appreciated by those of ordinary skill in the art having the benefit of the present disclosure, in certain illustrative embodiments the central processor may contain machine-readable instructions that enable it to perform the methods disclosed herein.
[0043] Further, as would be appreciated by those of ordinary skill in the art, having the benefit of the present disclosure, the methods and systems disclosed herein may be used in conjunction with any type of bank notes. Accordingly, the term “bank note” as used herein is defined broadly to include the various types of bank notes known to those of ordinary skill in the art, such as, for example, bills made from polymers, cotton paper, regular paper, textiles or any other desirable fibers.
[0044] The invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive. Accordingly, the scope of the invention is established by the appended claims rather than by the foregoing description. All changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Further, the recitation of method steps does not denote a particular sequence for execution of the steps. Such method steps may therefore be performed in a sequence other than that recited unless the particular claim expressly states otherwise. | Methods and systems for automated detection of a transparent gap present between subsequent bank notes undergoing high-speed processing are disclosed. A system for distinguishing between bank notes in a bank note processing machine comprises a conveyance device for transporting a bank note along a transport path and a detector comprising an optical sensor and an ultrasonic sensor disposed at a desired location along the path. The optical sensor identifies a transparent region at the desired location and the ultrasonic sensor determines if the transparent region corresponds to a transparent gap. | 6 |
This application is a division of U.S. patent application Ser. No. 07/694,376, filed May 1, 1991, now U.S. Pat. No. 5,125,434.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for assembling the actuation elements of a rotating dobby.
2. History of the Related Art
Rotating dobbies for forming the shed in weaving looms are known to be constituted by the assembly, side by side, along a principal shaft driven in an intermittent movement of rotation with a stop every 180° , of a series of actuation elements which are placed under the control of a programmed reading device and of which each is connected to one of the heddle frames mounted on the corresponding loom.
The invention relates more particularly to rotating dobbies of the type disclosed in French Patent No. 2 596 425 of Mar. 26, 1986 to STAUBLI. As schematically shown in FIG. 1 of the accompanying drawings, which figure reproduces FIG. 1 of the Patent in question, the frame 1 supports the intermittently rotating principal shaft 2 which drives the actuation elements of the dobby. Each elements includes a connecting rod 3 coupled to a lever 4 connected to one of the frames 5 of the loom. Each connecting rod 3 has an opening therein in which is engaged, with the interposition of a roller bearing 6, an eccentric 7 mounted idly on shaft 2 via a roller bearing 8. In addition, there is associated with each connecting rod 3 a driver plate 9 which is secured to the shaft 2, provided to the splined to that end, and which has two opposite notches 9a therein, adapted to cooperate with a coupling hook 10 mounted on a small pin 11 carried by a projecting plate secured to the eccentric 7.
Pivoting of the hook against its return spring 12 is controlled by two selector levers 13 which pivot at 14 and which are coupled to one another by a small rod 15. With one of these levers 13 are associated two pivoting rods 16 that needles 17, placed under the control of a programmed reading device 18, conduct to a position such that the rods are or are not placed opposite the reciprocating stroke of two pushers 19. There is associated with one of the levers 13 a spring 20 which tends to maintain the opposite lever in abutment against a fixed stop 21.
When the hook 10 is subjected to the action of its spring 12, the eccentric 7 is coupled to shaft 2, with the result that the connecting rod 3 is pivoted by an oscillating movement which displaces the frame 5 vertically. On the contrary, when this hook receives the action of one of the levers 13, its outer edge comes into contact with a resiliently urged bolt 22 carried by a small fixed pin 23, with the result that it is immobilized and that it in turn immobilizes the connecting rod 3 shown.
In principle, such an arrangement makes it possible to obtain reliable functioning even at high speeds of rotation, but this advantageous result is obtained only with a drastic monitoring of the different elements constituting the actuation elements, this, in addition, involving very meticulous assembly operations. It will be readily appreciated that even the slightest defect in the positioning of the pivot pins 11 (hook 10) and 23 (bolts 22) or in the profile of the notches made in the plates 9 and in the back of the hook mentioned, automatically make correct functioning impossible.
It is a principal object of the present invention to overcome this drawback in conventional rotating dobbies.
SUMMARY OF THE INVENTION
The invention relates to a process for assembling the actuation elements of a rotating dobby, which process consists principally in mutually positioning the members of each of the actuation elements, so as to cause cooperation between a control hook or engaging element and the drive plate which is mounted on the drive shaft and between another engaging element which selectively connects an eccentric to a connecting rod. Thereafter, the assembly of elements is engaged on the principal drive shaft with their orientation thereon being aided by the connection of the connecting rods to the drawing lever which connects each connecting rod to the corresponding heddle frame. Finally, an axial tightening along the axis of the drive shaft is accomplished so that the driving plates, gripped between roller bearings of the eccentrics, are rigidly secured to the drive shaft.
It will be understood that such a process of assembly automatically overcomes all the faults likely to affect the positioning or profile of the members constituting the actuation elements
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be more readily understood on reading the following description with reference to the accompanying drawings, in which:
FIG. 1, as indicated hereinbefore, shows the arrangement of a known rotating dobby.
FIG. 2 a schematic transverse section through a rotating dobby according to the invention, this section showing the arrangement of each of the actuation elements mounted on the principal shaft.
FIG. 3 is a perspective view illustrating the reciprocal angular positioning of the members which constitute the same actuation element.
FIG. 4 is a axial section through the dobby.
FIG. 5 reproduces a detail of FIG. 4, on a larger scale.
FIG. 6 illustrates an alternate embodiment of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring again to the drawings, in FIG. 2, reference 24 designates the principal shaft of the dobby, which, while being driven by an intermittent movement of rotation with a stop every 180° , has a smooth wall. On shaft 24 are fitted the different actuation elements "A" of the dobby placed under the control of a reading device containing the weaving program for controlling the heddle frame "B" coupled to the elements.
As shown more particularly in FIG. 2, each element "A" compromises a connecting rod 25 of substantially triangular profile, of which the apex carries a pin 26 on which is articulated the end of a lever 27 which will be described hereinafter. The connecting rod 25 has a circular opening 25a therein (cf. FIG. 3) inside which is engaged, with the interposition of a roller bearing 28, an eccentric 29 mounted idly on the shaft 24 with the interposition of a roller bearing 30. The eccentric 29 is laterally secured to a plate 29a of which the suitably profiled outer edge has two diametrically opposite notches 29b therein.
Notches 29b are adapted to cooperate with the tip of a bolt 31 of which the base is provided with a lateral pivot pin 31a freely introduced in a performation made in the connecting rod 25, in the immediate vicinity of the edge thereof. A spring 32, abutting against a stop 33 mounted against the connecting rod 25, tends to urge the pivoting bolt 31 so that is tip engages in one or the other of the two notches 29b, resiliently ensuring the angular immobilization of the connecting rod 25 with respect to the eccentric 29 and vice versa.
Each actuation element "A" further comprises a driver plate 34 of which the periphery has two diametrically opposite notches 34a therein. With this driver plate 34 there is associated a pivoting hook 35 mounted on a lateral pin 29c extending from the plate 29a of the eccentric 29. A spring 36, bearing on a stop of the plate 29a, tends to engaged the norse or tip 35a of the hook 25 inside one or the other of the two notches 34a of the driver plate 34, which is thus positioned angularly with respect to the eccentric 29 at that same time as it is retained fixed relative thereto.
Control of the pivoting hook 35 against its spring 36 is effected by one or the other of two selector levers which have been schematically shown by arrows 37 in FIG. 2 but which are, in fact, similar to the two levers 13 of FIG. 1, being subjected to a programmed reading device. In addition, the functioning of the dobby is identical to that of the dobby of FIG. 1 and therefore requires n detailed description.
It will be noted that, according to the invention, the assembly of the levers 27, which are coupled to the connecting rods 25, and to tie-rods 38 connected to the heddle frames "B" are articulated on a fixed pin 39 (FIG. 2) carried by the frame of the dobby parallel to shaft 24.
FIG. 4 clearly shows the parallel assembly of shaft 24 and the pivot pin 39 between the two side plates 40 which form the frame mentioned above. One of these plates is equipped with a needle bearing 41 inside which is supported shoulder 24a of the shaft 24. It will be understood that the actuation elements "A" of the dobby are capable of being engaged on the shaft 24 by the roller bearings 30 and the driver plates 34 at the same time as the levers 27 are introduced on the pin 39. (In another embodiment, pin 39 may be introduced in the assembly of the actuation elements once the elements are on the shaft 24).
Such engagement on shaft and pin elements 24 and 39 ensures both suitable orientation of the elements "A" with respect to shaft 24 and to the heddle frames "B", and perfect positioning of the members constituting each element, since the driver plate 34 is connected by the hook 35 to the eccentric 29 which is itself connected to the connecting rod 25 by the bolt 31.
It then suffices to engage, on the end of the shaft 24 opposite the end supported by roller bearing 41, a cap 42 equipped with longitudinal screws 43 cooperating with corresponding tappings in shaft 24, and to tighten the screws 43. It will be understood that, if care has been taken to give the inner ring 30a of the roller bearings 30 an axial thickness slightly greater than that of the assembly formed by each eccentric 29 and its plate 29a, adjusting the screws 43 ensures, by application of the free edge of the cap 42 against the element "A" or an appropriate bearing washer, the efficient connection of the shaft 24 and the driver plates 34. The plates are gripped between the roller bearings 30, while the eccentrics 29 remain free to rotate, all this being clearly illustrated in FIG. 5.
The tightening cap 42 is supported by the corresponding side plate 40 of the dobby with the aid of a needle bearing such as the one shown at 44 in FIG. 4. A longitudinal pin 45 is provided between cap 42 and the shaft 24 so as to avoid any risk of rotational shifting between the two pieces.
In certain cases and in the manner illustrated in FIG. 6, the shaft 24 may be provided with a longitudinal key 46 adapted to oppose a considerable rotational shift of the driver plates 34 in case of defective tightening of the cap 42. The key 46 allow a clearance inside a notch 34b made in the opening of each plate in order to allow self-adjustment thereof during initial assembly. | A process for assembling the actuation elements of a rotating dobby, in which the connection between the driver plates of the different actuation elements and the driven shaft thereof is effected by axial tightening of the driver plates between an end cap and spaced bearings. Such tightening is effected once the drawing levers have been engaged on the pivot pin so that the members of each actuation element, which are selectively connected to one another by the coupling elements, are automatically properly positioned on the drive shaft. | 3 |
This application is a continuation of application Ser. No. 07/339,774, filed Apr. 18, 1989, abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to broadband antennas and, more specifically, to broadband antennas of compact size which are capable of receiving or transmitting multi-polarized electromagnetic radiation.
2. Brief Description of the Prior Art
Antennas are often required to receive or transmit electromagnetic radiation over several octaves of bandwidth while maintaining uniform radiation pattern and impedance characteristics within the operating band. Antennas of this type have been well known in the art for many years and include log periodic and spiral radiating structures. Often however, the polarization of the received electromagnetic signal is unknown and a conventional log periodic or spiral antenna may not respond to the sense of polarization being transmitted. The problem of responding to transmitted signals over a broad band for any sense of polarization (i.e. vertical, horizontal, left hand circular or right hand circular) is difficult and has not been completely solved in the prior art.
The most pertinent prior art of which applicants herein are aware is a patent to DuHamel (U.S. Pat. No. 4,658,262). This patent discloses a log periodic zig zag antenna having four identical zig zag members positioned 90 degrees apart. An RF processor consisting of two 180 degree Marchand baluns and a 90 degree hybrid, remote from the antenna, is used to feed a transmission line extending from a cavity in the base region of the antenna housing, upward along the antenna axis and attaching to the antenna central feedpoint.
A common failure mode of cavity backed antennas which are fed at the central feedpoint with a transmission line positioned on the antenna axis is that of mechanical separation between the antenna and transmission line. The failure usually occurs when the antenna is subjected to environmental stress such as thermal cycling or vibration. This problem exists because the thin circular antenna substrate, which is permanently attached to the cavity at its perimeter, acts as a diaphragm and moves up and down at the center (feed point region) due to thermal cycling and vibration. When this movement occurs, the antenna pulls loose from the transmission line attached to the central feedpoint, resulting in complete electrical failure. As will be demonstrated hereinbelow, the present invention eliminates this problem because the antenna transmission line is attached at the perimeter of the antenna (diaphragm) where there is no movement between the antenna and the feeding transmission line and, thus, there is far less stress at the antenna/feed connection interface.
SUMMARY OF THE INVENTION
The present invention provides, the above noted desired properties of a broadband unidirectional antenna response, independent of polarization, with concomitant freedom from mechanical feedpoint failure.
Briefly, this is accomplished by providing two printed circuit interleaved log periodic dipole elements disposed orthogonal to each other. The interleaved log periodic elements are etched on a dielectric substrate and placed over an absorber loaded cavity backing to provide unidirectional broadband performance similar to that of a cavity backed planar spiral antenna. The log periodic elements are preferably, but not limited to, a copper etched circuit and the dielectric (electrically insulating) substrate is preferably, but not limited to Fiberglas or polytetrafluoroethylene (Teflon) glass (e.g. Duroid type 5880). The interleaved log periodic elements are in the form of circular arcs to efficiently utilize the available space in the circular aperture. The radial distance from the antenna center to the inner (rn) and outer (Rn) arcs of each of the dipole arms is scaled by a constant factor tau, wherein tau=R.sub.(n+1) /R n as shown in FIG. 1. The degree of interleaving is controlled by an angle alpha wherein, as alpha increases, interleaving becomes greater. The sigma symbol in FIG. 1 controls individual element width. The term w is the width of the transmission line transporting RF energy to and from each of the radiating elements of the antenna wherein change in w will change the impedance of the transmission line.
Furthermore, the antenna in accordance with the present invention is connected to the feeding transmission line at the antenna perimeter rather than at the central antenna feedpoint as is common for other cavity backed broadband antennas, including that of the nearest known prior art described in DuHamels U.S. Pat. No. 4,658,262. This offers a distinct reliability advantage.
Briefly, this is accomplished by having the energy received by the antenna enter at the antenna active region (approximately the one wavelength circumference region) and flow from the central antenna feedpoint radially outward therefrom to the outer perimeter of the antenna substrate (diaphragm) via a pair of orthogonal printed circuit (coaxial, microstrip or stripline) baluns. These baluns, (commonly called infinite baluns because of their unlimited bandwidth) are an integral part of the etched antenna substrate and replace the need for two separate Marchand baluns as described in DuHamel's U.S. Pat. No. 4,658,262. At the outer perimeter of the antenna, baluns are connected to a coaxial line which transports the received signal to the printed circuit 90 degree hybrid located at the base region of the antenna. The outputs of the 90 degree hybrid provide left hand circular and right hand circular polarized ports.
If only dual linear (horizontal and vertical) polarizations are required, the outputs may be taken directly off of the balun ports without need for the 90 degree hybrid. Thus, the antenna has multiple polarized capability for a single radiating aperture. For some applications, it may be required that the antenna have only one output port, yet have dual polarized capability. This is accomplished by incorporating a single pole two throw PIN diode, FET or mechanical switch between the 90 degree output ports of the hybrid and the single antenna output port. The switch in the described embodiment consists of a PIN diode type commonly available from a microwave component supplier such as M/A-COM Semiconductor Products of Burlington, Mass. 01803. All of the components of the invention including antenna radiating aperture (interleaved log periodic dipole elements), polarization processor (printed circuit infinite baluns, 90 degree hybrid with coaxial interface), absorber loaded antenna cavity and polarization selection switch are housed in a single housing.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 details the geometry defining a single element of the interleaved log periodic structure;
FIG. 2 shows the interleaved geometry of the Compact Multi-Polarized Broadband Antenna radiating aperture;
FIGS. 3(a) and 3(b) show the excitation required to obtain left hand and right hand circular polarizations for a four terminal symmetrical antenna feed point as used in this invention;
FIG. 4 shows a common method of feeding four symmetrical feed points to obtain left hand and right hand circular polarization, the accepted practice being to have these components remote from the antenna radiating aperture. For the invention described herein, the two baluns are an integral part of the printed circuit antenna radiating aperture for improved reliability and reduced cost;
FIG. 5 shows an exploded view of the antenna components and their relative position to each other;
FIG. 6 shows a top view of the 90 degree hybrid and polarization switch;
FIG. 7a is a first means of implementing the center antenna feedpoint with microstrip or printed circuit baluns employing a shorting pin or plated through hole shown in detail in FIG. 7b.
FIG. 7c is a second means of implementing the center antenna feedpoint with microstrip or printed circuit baluns employing a completely solderless feed region geometry shown in detail in FIG. 7d.
FIG. 8a shows the detail of how the orthogonal feed geometry crosses over at the central feedpoint region;
FIG. 8b is an exploded view of the feed region of FIG. 8a.
FIGS. 9(a) and 9(b) show measured left and right hand circular polarized radiation patterns at a single frequency;
FIG. 10 shows a capacitively loaded interleaved log periodic antenna capable of simultaneous SUM and DIFFERENCE radiation pattern operation. This loading approach also is useful for the four port SUM mode antenna shown in FIG. 2 for applications where size reduction is a requirement;
FIG. 11 shows the geometry for a conventional stripline circuit; and
FIGS. 12(a) to 12(e) show the geometry for a stripline fed interleaved log periodic antenna.
DESCRIPTION OF PREFERRED EMBODIMENTS
Functional Description--The basic functional components of the antenna assembly are shown in FIG. 5 and consist of: (1) the interleaved log periodic radiating aperture with integral printed circuit infinite baluns which are part of the polarization processor, (2) absorber loading consisting of: (a) the absorber loaded antenna cavity for broadband unidirectional pattern performance, and (b) the termination absorber around the antenna perimeter for enhanced low frequency performance, (3) the polarization processor consisting of: (a) the printed circuit infinite baluns (integral to the radiating structure) and (b) the 90 degree hybrid and (4) the antenna housing and radome cover.
The polarization processor provides appropriate antenna feedpoint excitations, see FIGS. 3(a) and 3(b), at the four antenna feedpoints located at the center of the radiating aperture. These excitations require equal amplitude at all four antenna feedpoints and sequential phase progressions in increments of 90 degrees for both clockwise and counter clockwise rotations. This excitation provides both left hand and right hand circular polarized antenna outputs from the 90 degree hybrid. The antenna assembly is housed in a metallic cup shaped housing and covered with a dielectric (Fiberglas) radome for environmental protection.
Detailed Description--Referring first to FIG. 1, there is shown the geometry which describes a printed circuit log periodic structure. Log periodic antennas are discussed in greater detail in the literature, e.g. Antenna Handbook by Y. T. Lo and S. W. Lee, Chapter 9, Frequency Independent Antennas, 1988 Van Nostrand Reinhold Co. Inc. The log periodic geometry is used to lay out an antenna by first defining an antenna element within a single cell, (e.g., between R 1 and r 1 and between alpha equal to zero and alpha). The same configuration of conductor, properly scaled by the constant scale factor tau, is then reproduced in the other cells. If this process is repeated infinitely many times for smaller cells, the resulting geometry will converge to a point. Likewise, infinite repetition of the larger cells will cause the structure to become infinitely large.
FIG. 2 shows a top view of the unique interleaved log periodic dipole geometry employed in this invention. For the configuration shown in FIG. 2, log periodic dipole sets 1 and 2 are fed with equal amplitude and phase of 0 degrees and 180 degrees respectively at the center feedpoint by microstrip baluns 5 and 7. Likewise, log periodic dipole sets 3 and 4 are fed with equal amplitude and a phase of 90 degrees and 270 degrees respectively at the center feedpoint by microstrip baluns 6 and 8, FIGS. 3a and 3b show the required antenna feedpoint excitations at the center of the antenna to obtain right hand circular LHCP and left hand circular RHCP polarizations.
FIG. 4 shows the conventional manner in which the appropriate excitation is obtained for dual sense circular polarization. This consists of two separate 180 degree hybrids or baluns plus a separate 90 degree hybrid. The described embodiment herein eliminates the two separate 180 degree hybrids or baluns by incorporating them as an integral part of the antenna etched circuit for improved reliability, producibility and lower cost.
In FIG. 5 is shown an exploded view of the antenna assembly of a preferred embodiment in accordance with the present invention. For this preferred embodiment, log periodic antenna elements 31 and 33 are etched on opposite sides of antenna substrate 32. The etched log periodic antenna circuit accommodates orthogonal printed circuit microstrip baluns which lie radially along the center of each set of log periodic elements. These printed circuit baluns are an integral part of the etched log periodic geometry. The orthogonal printed circuit baluns transport energy from the central antenna feed point to the signal extraction points 40 and 41 of FIG. 5, at the antenna perimeter. Coaxial lines 36 and 37 which are connected to remote signal extraction points 40 and 41 of FIG. 5 transport RF energy received by the antenna downward to the 90 degree hybrid consisting of layers 11, 12 and 13. Mode suppressing collars 34, 35, 38 and 39 are used to suppress unwanted higher order modes and launch the received RF signal from the printed circuit antenna balun onto the coaxial line and from the coaxial line onto the stripline 90 degree hybrid. The 90 degree hybrid consists of a dielectric substrate (0.010 inch thick Duroid 5880) 12 and RF coupler circuits 11 and 13 etched on opposite sides of the substrate 12. The 90 degree coupler stripline circuit is completed by the dielectric layers 10 and 14 which are (0.031 inch thick layers of Duroid 5880) metallized on the outside surfaces to form a 90 degree hybrid stripline circuit. The metallized surface of the upper dielectric layer 10 serves as the metallic base for the absorber loaded cavity 17. Design of the 90 degree coupler follows standard methods commonly used by those skilled in the art. The load ring 24 acts as a termination at the outer perimeter of the antenna structure to reduce reflections at the lower operating frequencies. This load ring is made of a carbon loaded epoxy resin and is painted on to the antenna substrate. The structure 15 is the baseplate for the internal antenna/processor/switch subassembly. The subassembly is attached to this base plate 15 to assist in holding it together prior to dropping into the cavity 17. The subassembly is dropped into cavity 17 to make the final assembly. The device 22 is the RF output connector.
The antenna herein described, operates over a bandwidth limited at the high frequencies by physical detail at the central feed region and at the low frequencies by the physical size of the structure. The antenna by itself is a bidirectional radiating element. Because unidirectional radiation is preferred, the antenna is backed by an absorber loaded cavity. The absorber used is graded to allow a gradual transition from a relatively low dielectric constant and low electrical loss material 19, to a medium dielectric constant and medium loss material 20, to a higher dielectric constant and high loss material 21. This allows the back radiation of the antenna to be absorbed with a minimum of reflection from the absorber surface, resulting in uniform pattern and gain performance over the operating band. Typical of the absorbers which can be used for materials 19, 20 and 21 are Emerson and Cumming Co. types LS22, LS24, and LS26. Additionally, a carbon loaded honeycomb absorber, also available from Emerson and Cumming, will work and provide a structural support for the antenna. The antenna performance can be improved by having a 0.125 inch air space between the antenna and the absorber layer 19. In practice, this space can be a structural foam spacer, such as styrofoam, which electrically is similar to air, but yet provides structural support for the antenna. The antenna is dropped into an aluminum cup shaped housing 17 and covered with a dielectric radome 23 for environmental protection.
FIG. 6 shows a top view of the 90 degree hybrid coupler assembly 11, 12, and 13 plus the polarization selection switch 16 and the polarization switch which provides either RHCP or LHCP to a single output port at the base of the antenna.
There are various means of implementing the detailed feed geometry at the center of the antenna structure. One method is to have the log periodic elements all on one side of the antenna substrate and fed with a printed circuit microstrip or stripline balun as illustrated in FIG. 7a and 7d. In this configuration, the microstrip balun conductor on the underside of the substrate must bridge the center feed point gap and connect to the log periodic elements on the left side of the structure by means of a shorting pin or a plated through hole. The shorting pin or plated through hole can be eliminated by placing the log periodic elements on the left side of the structure under the substrate as is illustrated in FIGS. 7c and 7d by dashed lines. Here, the microstrip balun conductor which is on the under side of the substrate, bridges the feed point gap and connects directly to the log periodic elements on the left side of the structure.
The feed points described in FIGS. 7a to 7d can be physically realized for crossed orthogonal log periodic elements as shown in FIGS. 8a and 8b. For this arrangement, the orthogonal microstrip baluns are etched on opposite sides of the antenna substrate. The orthogonal geometry keeps the coupling between the baluns to a minimum. Thus, a solderless feedpoint or a feedpoint using the shorting pins can be realized. The key point is that for either case, the feed region at the center of the antenna is not attached to a transmission line running through the antenna cavity to the 90 degree coupler in the antenna base. This is important because the embodiment of this invention is far more reliable than that of conventional cavity backed designs of prior art. FIG. 9 shows typical radiation patterns for right hand and left hand circular outputs.
Alternate Embodiments--FIGS. 5 and 7a to 7d describe a configuration where the antenna is fed by means of two orthogonal microstrip infinite baluns. An alternate feeding method, is to employ two orthogonal infinite baluns in the form of a stripline circuit in lieu of the microstrip balun circuit. A conventional stripline circuit is shown in FIG. 11 where the center conductor 41 of the stripline circuit is suspended between ground planes 42 and 43 by means of dielectric substrates 44, 45, and 46. The stripline circuit shown in FIG. 11 is extended to the integrated infinite balun of the interleaved log periodic antenna as shown in FIGS. 12(a) to 12(e).
Referring to FIG. 12(a) to 12(e), two orthogonal and radial stripline feeds 53 and 57 are contained on opposite sides of a very thin (approximately 0.006 inch) dielectric substrate 52. Radial stripline feeds 53 and 57 are contained between conductors 51 and 54 plus 55 and 58 respectively. The center stripline conductors 53 and 57 bridge a small gap 60 at the center feed point (see exploded view in FIG. 12(a)) and connect to radial feed lines 59 and 62 plus 61 and 63 respectively via a shorting pin or plated through hole. The log periodic pattern is etched and registered on upper and under sides of the substrate 63 and 64. The stripline fed antenna is connected to the coaxial feeding transmission line at the outer perimeter of the structure in a similar manner to that shown in FIG. 5. In FIG. 5, the coaxial transmission line center conductor connects to the microstrip (stripline) center conductor and the coaxial transmission line shield connects to the log periodic elements at the outer perimeter. For either the microstrip or stripline feed method, the key reliability feature is retained because no transmission line passing along the antenna axis, perpendicular to the plane of the antenna, is connected to the central antenna feed point. Thus, the antenna is free to move up and down (diaphragm action) due to environmental conditions without causing feedpoint failure.
Another variation of the integrated printed circuit microstrip or stripline balun (which is an integral part of the antenna substrate) is to extend or continue the balun and substrate past the perimeter of the antenna elements. In this case the balun forms a flex circuit which may connect to the 90 degree hybrid, polarization selection switch or two dual output ports for dual linear operation.
Dual Mode Performance--The four orthogonal log periodic structures described in the previous paragraph are capable of providing a SUM pattern performance only, e.g. (peak of beam on the antenna axis) independent of frequency and polarization. For monopulse DF (direction finding) applications it is desirable to have a single antenna aperture capable of radiating both SUM and DIFFERENCE patterns simultaneously. The DIFFERENCE pattern has a null on the axis of the antenna. It is not possible to obtain a circular polarized DIFFERENCE pattern with four orthogonal linear polarized elements as shown in FIG. 2. In order to obtain a circular polarized difference pattern with linear polarized elements, one must employ a minimum of six linear polarized elements arranged in a hexagonal geometry Referring to FIG. 2, it becomes obvious that if one were to introduce six log periodic elements, the radial feed lines would interfere with the interleaved geometry. Thus, the geometry as shown in FIG. 2 is not suitable for six interleaved log periodic elements without some special design features.
Shown in FIG. 10 is the new design of log periodic elements which are foreshortened by means of capacitive loading. The capacitive loading tabs 74 foreshorten the log periodic dipole elements and allow six radial feeds to converge at a central feed point region 75. The capacitive loading tabs allow size reduction of the log periodic dipole elements by as much as 60 percent. For dual mode performance, the six ports must be feed with a six port RF processor capable of exciting both SUM and DIFFERENCE modes. For one sense of polarization of the SUM mode, the processor must feed each of the six feed ports with equal amplitude and a sixty degree phase progression around the feed region, e.g., 0, 60, 120, 180, 240, and 300 degrees. For the opposite sense of circular polarization of the SUM mode, the phase sequence is reversed, e.g., 0, 300, 240, 180, 120, and 60 degrees. For one sense of polarization of the DIFFERENCE mode, the processor must feed each of the six ports with equal amplitude and a one hundred twenty degree phase progression (twice that for the SUM mode) around the feed region, e.g., 0, 120, 240, 360, 480, and 600 degrees. For the opposite sense of circular polarization of the DIFFERENCE mode, the phase sequence is reversed, e.g., 0, 600, 480, 360, 240, and 120 degrees. Thus it is possible to realize a single antenna aperture capable of providing dual sense circular polarization for both SUM and DIFFERENCE modes for monopulse direction finding applications.
An additional benefit of the capacitive loading (foreshortening) technique illustrated in FIG. 10 is that of size reduction of the radiating aperture. This allows a dual polarized aperture to be electrically large for low frequency performance where the wavelength is long and physically small. This is attractive for many airborne applications where installation space constraints are critical.
Though the invention has been described with respect to specific preferred embodiments thereof, many variations and modifications will immediately become apparent to those skilled in the art. It is therefore the intention that the appended claims be interpreted as broadly as possible in view of the prior art to include all such variations and modifications. | The disclosure relates to a multipolarized broad band antenna and antenna system wherein the antenna structure is formed on a substrate, the antenna structure on the substrate including a central feedpoint, a first antenna element having a plurality of regions composed of first plural interconnected concentric sectors of circles of diminishing radius extending to the feedpoint, and a second antenna element having a plurality of regions composed of second plural interconnected concentric sectors of circles of diminishing radius extending to the feedpoint, the second plural concentric sectors being interleaved with the first plural concentric sectors. | 7 |
BACKGROUND OF THE INVENTION
[0001] This application relates in general to scanning devices and in particular to a portable scanning apparatus able to operate independently of a host system.
[0002] Portable bar code scanners are known in the art. Most such scanners have a size and form factor suitable for being held comfortably in the hand of a human operator. This device size may be suitable for applications such as scanning bar codes in supermarkets or other environments in which an employee is expected to carry work-related equipment around. However, the portability and flexibility of a scanner of this size may be limited outside the context of the work environment described above.
[0003] Accordingly, there is a need in the art for a scanner having more flexibility than what is currently available in the art.
SUMMARY OF THE INVENTION
[0004] According to one aspect, the present invention is directed to a portable scanning apparatus that may include a bar code scanner module incorporated within a housing; a portable computer memory assembled to the bar code scanner and incorporated within said housing, wherein the computer memory is operable to receive and store data obtained by the bar code scanner, and wherein the assembly of the bar code scanner and the portable computer memory within said housing forms a compact and portable package.
[0005] Other aspects, features, advantages, etc. will become apparent to one skilled in the art when the description of the preferred embodiments of the invention herein is taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] For the purposes of illustrating the various aspects of the invention, there are shown in the drawings forms that are presently preferred, it being understood, however, that the invention is not limited to the precise arrangements and instrumentalities shown.
[0007] FIG. 1 is a plan view of a memory stick scanner in accordance with an embodiment of the present invention;
[0008] FIG. 2 is a perspective view of a scanner module in accordance with an embodiment of the present invention;
[0009] FIG. 3 is a plan view of the scanner module of FIG. 2 ; and
[0010] FIG. 4 is a block diagram of a computer system useable in conjunction with an embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0011] In the following description, for purposes of explanation, specific numbers, materials and configurations are set forth in order to provide a thorough understanding of the invention. It will be apparent, however, to one having ordinary skill in the art that the invention may be practiced without these specific details. In some instances, well-known features may be omitted or simplified so as not to obscure the present invention. Furthermore, reference in the specification to phrases such as “one embodiment” or “an embodiment” means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. The appearances of phrases such as “in one embodiment” or “in an embodiment” in various places in the specification do not necessarily all refer to the same embodiment.
[0012] FIG. 1 is a plan view of a portable scanning system 10 in accordance with an embodiment of the present invention. Scanning system 10 may include memory stick (also known as a thumb drive) 100 , scanner module 200 , and/or battery 300 , which is preferably rechargeable. Scanning system 10 may periodically be connected to computing system 400 to upload and/or download data, and/or to charge battery 300 . Computing system 400 is discussed in greater detail in connection with FIG. 4 .
[0013] Scanning apparatus 10 preferably has a form factor that is longer (where length is the left-to-right dimension in FIG. 1 ) than it is wide (where width is the up-down dimension in FIG. 1 ). Moreover, scanning apparatus 10 may be sized so as to: (a) fit into a pocket, such as shirt pocket or pants pocket; (b) be attachable to a neck strap; and/or (c) be attachable to a standard personal keychain without being unduly cumbersome.
[0014] Memory stick 100 may be used to receive and store scan data from scanner module 200 . Memory stick 100 may also be used to store operational data for scanner module 200 , which may be delivered to scanner module 200 as needed. For instance, if different operating conditions and different scanning tasks require different scan speeds, different lighting, and/or different analog scan data processing (such as, for instance, using different thresholds for distinguishing between a logic “0” level and a logic “1” scan data value), then an entire range of scanner module operating data could be stored in memory stick 100 , in computing system 400 , or in a combination of the foregoing.
[0015] Battery 300 may be rechargeable, but need not be. Disposable batteries may be employed instead. Battery 300 may be configured so as to be removable from scanning apparatus 10 for recharging purposes, and/or to enable a substitute battery to installed within scanning apparatus 10 . However, alternatively, scanning apparatus 10 could be configured so that a rechargeable battery 300 is permanently affixed within scanning apparatus 10 .
[0016] Scanning system 10 may further include connector 110 (for connecting to host computer 400 , or other computing system) and/or activation button 120 . Memory stick 100 may include Random-Access Memory (RAM), Read-Only Memory (ROM), Flash memory, or any combination of the foregoing. Any suitable type of memory devices may be used for the RAM or ROM memory circuits. Moreover, the present invention is not limited to above-listed memory types. In one alternative embodiment, scanning system 10 could include a Radio Frequency (RF) transceiver for transmitting scan data wirelessly to another device from scanning system 10 and/or for transmitting data to scanning system 10 from a remotely located device. Memory stick 100 may be used to store scan data obtained by scanning module 200 . However, memory stick 100 preferably includes enough data storage capacity to store a large amount of data from sources other than scanning module 200 .
[0017] FIG. 2 is a perspective view of scanner module 200 in accordance with an embodiment of the present invention. Scanner module 200 may include laser diode 202 , focusing lens 204 , bending mirror 206 , laser beam 208 , motor 208 , motor 210 , printed circuit board 212 , polygon mirror 214 , and/or detector 216 . Moreover, scanner module 200 may be powered either by battery 300 ( FIG. 1 ), by a power source in a docking station such as computing system 400 , or by a combination of the foregoing. FIG. 3 is a plan view of scanner module 200 of FIG. 2 . Suitable connections may be implemented (not shown) to convey signal data from detector 216 to electronic circuitry on scanner module 200 (or on a device in communication with scanner module 200 ) to receive, process, and store scan data from detector 216 , as is known in the art.
[0018] The scanner module shown in FIGS. 2 and 3 is exemplary. The present invention is not limited to the specific implementation of scanner module shown therein. Any one of several possible configurations of a modern scanner could be used in conjunction with a memory stick in embodiments of the present invention.
[0019] When not connected to a host device, scanning apparatus 10 preferably runs on power from battery 300 which may be rechargeable and/or removable from scanning apparatus 10 . In this mode of operation, a human operator may initiate operation of scanner module 200 by pressing button 120 . Scanner module 200 may then scan a bar code, or other image, and receive scan data from the image. The scan data may then be digitized and stored either in memory within scanner module 200 or in memory stick 100 . Computational power sufficient to operate scanner module 200 and to coordinate the transfer of data to memory stick 100 may be incorporated within a processor within scanning apparatus 10 . This processor (not shown) may be incorporated within scanner module 200 , or within memory stick 100 . Alternatively, some data processing capability may be incorporated within processors within both memory stick 100 and scanner module 200 . Scanning apparatus 10 may continue operating in this mode until battery 300 needs recharging or replacement, or until memory stick 100 has no more storage space.
[0020] Scanning apparatus 10 may be connected to a host device such as computing system 400 . When connected in this manner, scanning apparatus 10 , and particularly the memory stick 100 portion thereof, may be configured to appear to a host system, such as computing system 400 , as an external drive having data accessible by the host system.
[0021] Scanning apparatus 10 may be configured to self-install upon being connected to a host system such as computing system 400 . At least one conductive path between computing system 400 and scanning system 10 may be used to charge battery 300 . Separately, scanning system 10 may upload stored scan data from scanning module 200 and/or memory stick 100 to a memory device within computing system 400 . Scanning system 10 may also download data from a host device, which data could include ordinary payload data for storage in memory stick 100 which is not relevant to scanner module 200 . Scanning system 100 could also download data that includes operational parameters for the operation of scanner module 200 .
[0022] FIG. 4 is a block diagram of a computing system 400 adaptable for use with one or more embodiments of the present invention. For instance, computing system 400 may serve as a host computer to which scanning system 10 may be coupled to. Moreover, a computing system incorporating one or more of the components (depicted with individual blocks in FIG. 4 ) may be incorporated within scanner module 200 to store operational data for controlling the scanning operation (i.e. to control motor speeds, do initial processing on scan data, etc.), to store scan data received at detector 216 , to control data transfer between scanner module 200 and memory stick 100 , and/or other functions useful for the operation of scanning apparatus 10 .
[0023] In computing system 400 , central processing unit (CPU) 402 may be coupled to bus 404 . In addition, bus 404 may be coupled to random access memory (RAM) 406 , read only memory (ROM) 408 , input/output (I/O) adapter 410 , communications adapter 422 , user interface adapter 406 , and display adapter 418 .
[0024] In an embodiment, RAM 406 and/or ROM 408 may hold user data, system data, and/or programs. I/O adapter 410 may connect storage devices, such as hard drive 412 , a CD-ROM (not shown), or other mass storage device to computing system 400 . Communications adapter 422 may couple computing system 400 to a local, wide-area, or global network 424 . User interface adapter 416 may couple user input devices, such as keyboard 426 , scanner 428 and/or pointing device 414 , to computing system 400 . Moreover, display adapter 418 may be driven by CPU 402 to control the display on display device 420 . CPU 402 may be any general purpose CPU.
[0025] It is noted that the methods and apparatus described thus far and/or described later in this document may be achieved utilizing any of the known technologies, such as standard digital circuitry, analog circuitry, any of the known processors that are operable to execute software and/or firmware programs, programmable digital devices or systems, programmable array logic devices, or any combination of the above. One or more embodiments of the invention may also be embodied in a software program for storage in a suitable storage medium and execution by a processing unit.
[0026] Although the invention herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It is therefore to be understood that numerous modifications may be made to the illustrative embodiments and that other arrangements may be devised without departing from the spirit and scope of the present invention as defined by the appended claims. | A portable scanning apparatus is disclosed, which may include a bar code scanner module incorporated within a housing; a portable computer memory assembled to the bar code scanner and incorporated within said housing, wherein the computer memory is operable to receive and store data obtained by the bar code scanner, and wherein the assembly of the bar code scanner and the portable computer memory within said housing forms a compact and portable package. | 6 |
RELATED APPLICATIONS
[0001] This application is a division of prior application Ser. No. 11/478,858, filed on Jun. 30, 2006, entitled DEVICE COMPRISING A FIELD OF TIPS USED IN BIOTECHNOLOGY APPLICATIONS which application claims the priority benefit of French Patent application No. 05/52044, filed on Jul. 5, 2006, which applications are hereby incorporated by reference to the maximum extent allowable by law.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a method for manufacturing a device comprising a field of micrometric tips. Such devices are used in biotechnology experiments as a support for the culture, the analysis, or the manipulation of biological cells.
[0004] 2. Discussion of the Related Art
[0005] FIGS. 1A to 1D are cross-section views of structures obtained in successive steps of a known method for manufacturing a device comprising a field of micrometric tips.
[0006] In an initial step, illustrated in FIG. 1A , an etch mask formed of an assembly of blocks 1 , 2 , and 3 spaced apart from one another and arranged in a matrix is formed on a substrate 1 . The substrate is, for example, a silicon wafer and the etch mask is formed of resin or of a silicon oxide layer.
[0007] In a next step, illustrated in FIG. 1B , an isotropic etching of the upper portion of substrate 1 is performed. The areas of substrate 1 not covered by blocks 2 , 3 , 4 are etched, as well as the lateral portions of the areas covered with blocks 2 , 3 , and 4 which are located close to the exposed areas. The etch time is provided for the “horizontal” etching under blocks 2 , 3 , 4 to be stopped when there only remain small unetched substrate portions under blocks 2 , 3 , 4 . However, to ensure the holding of blocks 2 , 3 , and 4 , that is, to avoid for them to fall, the remaining substrate portions must be sufficiently wide.
[0008] In a next step, illustrated in FIG. 1C , blocks 2 , 3 , and 4 of the etch mask are eliminated. A field of “truncated” tips 5 , 6 , and 7 is then obtained at the surface of substrate 1 . The tip height is of one or a few microns and the inter-tip distance at least six times as large as the height of the truncated tips. The tip density then is of from 1 to 2 tips on a 100 μm 2 surface area.
[0009] FIG. 1D is a cross-section view of a portion of a device comprising a field of tips obtained according to the previously-described method and on which biological cells are placed. The average diameter of a biological cell being 15 μm, each cell is laid on a few tips of the device, between 3/4 tips and some ten according to the cell shape.
[0010] A disadvantage of such a device is that it comprises tips of low height which are, what is more, truncated, that is, non-sharp. Such tips cannot be used to perform transfection operations consisting of piercing live cells to introduce into them elements, such as viruses, previously laid on the tips.
SUMMARY OF THE INVENTION
[0011] An object of the present invention is to provide a method for manufacturing a device comprising a field of micrometric tips having very sharp tips that enable performing transfection operations.
[0012] Another object of the present invention is to provide such a method which is easy to implement.
[0013] Another object of the present invention is to provide such a method which enables obtaining a device exhibiting a high density of tips.
[0014] To achieve these and other objects, the present invention provides a method for manufacturing a device comprising a field of micrometric tips comprising the steps of forming a polycrystalline layer on a support; performing an anisotropic plasma etching of all or part of the polycrystalline layer by using a gas mixture comprising chlorine and helium, whereby tips are formed at the surface of the polycrystalline layer.
[0015] According to an embodiment of the present invention, in the plasma etching, the gas flow rate of chlorine is higher than that of helium, the gas flow rate of helium for example being 130 cm 3 /minute and the helium flow rate being 70 cm 3 /minute.
[0016] According to an embodiment of the present invention, the polycrystalline layer comprises silicon.
[0017] According to an embodiment of the present invention, the support is a semiconductor substrate, such as a silicon substrate, covered with an insulating layer, such as a silicon oxide layer.
[0018] According to an embodiment of the present invention, the method comprises, prior to the plasma etch step, a deposition of a protection layer on the polycrystalline layer and the forming of through openings in the protection layer, tips being then formed at the surface of the polycrystalline layer inside of said openings.
[0019] According to an embodiment of the present invention, the method comprises, prior to the plasma etch step, an etching of the polycrystalline layer to form polycrystalline blocks, tips being then formed at the surface of the polycrystalline blocks.
[0020] According to an embodiment of the present invention, the method further comprises the forming according to a conformal deposition method of conductive films on the tips covering the polycrystalline blocks, each conductive film covering the tips of a crystal block extending in a conductive track placed on said support.
[0021] According to an embodiment of the present invention, the top diameter of the tips is at least ten times smaller than the tip height, the top diameter of the tips for example being 100 nm and the height of the tips for example being 10 μm, and the tip density is greater than 10 tips on a 100 μm 2 surface area.
[0022] The present invention also provides a device comprising at least one field of micrometric tips formed at the surface of a polycrystalline block placed on a support, each tip field being covered with a conductive film extending in a conductive track placed at the surface of the support and extending to reach a contact terminal.
[0023] According to an embodiment of the present invention, the device comprises a multitude of tip fields formed on crystal blocks arranged in a matrix.
[0024] According to an embodiment of the present invention, the device is used to evaluate the activity of biological cells placed on the tip fields of the device, a measurement device being connected to the contact terminals.
[0025] The foregoing and other objects, features, and advantages of the present invention will be discussed in detail in the following non-limiting description of specific embodiments in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] FIGS. 1A to 1D are cross-section views of structures obtained at the end of successive steps of a method, previously described, of manufacturing of a device comprising a field of micrometric tips;
[0027] FIG. 2 is a diagram of an etch apparatus in which is implemented part of the manufacturing method according to the present invention;
[0028] FIGS. 3A and 3B are cross-section views of examples of devices obtained at the end of the manufacturing method according to the present invention;
[0029] FIG. 3C is a cross-section view of a small part of the tip field of a device obtained according to the method of the present invention on which a biological cell is placed;
[0030] FIGS. 4A to 4D are cross-section or perspective views of structures obtained at the end of successive steps of an embodiment of the method according to the present invention; and
[0031] FIGS. 5A to 5D are cross-section or perspective views of structures obtained at the end of successive steps of another embodiment of the method according to the present invention.
DETAILED DESCRIPTION
[0032] For clarity, the same elements have been designated with the same reference numerals in the different drawings. Further, the various drawings are not to scale.
[0033] The method of the present invention enables forming a tip field at the surface of a polycrystalline layer according to an etch method that provides a multitude of tips at the surface of the polysilicon layer.
[0034] FIG. 2 is a diagram illustrating an etch device in which a support wafer 10 covered with a polycrystalline layer 11 is placed. This device enables performing an anisotropic plasma etching of polycrystalline layer 11 .
[0035] According to an aspect of the present invention, the gaseous plasma used to etch polycrystalline layer 11 contains chlorine and helium. The gaseous mixture may contain other neutral or catalyst elements.
[0036] FIGS. 3A and 3B are cross-section views of examples of devices comprising a field of tips 15 obtained according to the previously-described method. The tip height is substantially proportional to the etch duration, or at least increases according to said duration. According to whether crystal layer 11 is thin or thick, the tips are formed across the entire thickness of the crystal layer or in the upper portion thereof, as respectively visible in FIGS. 3A and 3B .
[0037] According to the method of the present invention, it is possible to manufacture “large” tips having a height of 10 μm or more. Further, the obtained tips are “sharp” and exhibit at their end a diameter lower than 100 nm.
[0038] It should further be noted that the obtained tips are very close to one another. There thus is a high density of tips. For tips with a height of approximately 10 μm, the density is of several tens of tips, 30 or 40, for a 100 μm 2 surface area.
[0039] FIG. 3C is an enlarged cross-section view of the tips of a device obtained according to the method of the present invention, on which a biological cell 16 is placed. Due to the thinness of tips 15 and to their density, it is possible to “pierce” the cell in many locations. Further, the tips can penetrate deep into the cell and reach its nucleus.
[0040] Thus, a device obtained according to the method of the present invention enables performing transfection operations. For this purpose, the elements which are desired to be introduced into cells are deposited on tip field 15 prior to the placing of the cells on the tips. Given the thinness of the tips and their density, the external cell membrane does not resist and pierces. The introduction of tips into the cells enables bringing into the cells elements covering the tips down to the nucleus of the “impaled” cells.
[0041] A detailed example of implementation of the method according to the present invention is described hereafter in relation with FIGS. 4A to 4D .
[0042] In an initial step, an insulating layer 21 is formed on a substrate 20 . Substrate 20 may be a silicon wafer and insulating layer 21 may be a silicon oxide layer, for example having a 500-nm thickness.
[0043] At the next step illustrated in FIG. 4B , a polycrystalline layer 22 is formed on insulating layer 21 . For this purpose, the entire polycrystalline layer may be formed according to a chemical vapor deposition method. It is also possible to form a thin bonding layer by chemical vapor deposition, then to grow the rest of the layer in an epitaxial furnace. Polycrystalline layer 22 may be a silicon or silicon/germanium layer. The thickness of polysilicon layer 22 is selected according to the height of the tips which are desired to be subsequently formed, where the thickness of the polysilicon layer naturally has to be at least equal to the desired tip height. A polycrystalline layer exhibiting a thickness greater than the height of the desired tips will preferably be provided so that tips are “anchored” in the lower, unetched portion of the polycrystalline layer.
[0044] In a next step, illustrated in FIG. 4C , a protective layer 23 is deposited on polycrystalline layer 22 . Through openings 25 and 26 are then formed in protective layer 23 , for example, according to an HF-based wet etch method. Protective layer 23 may be a silicon oxide layer obtained by thermal oxidation of silicon or silicon/germanium polycrystalline layer 22 . The thickness of protective layer 23 is, for example, 500 nm.
[0045] At the next step, illustrated in FIG. 4D , an anisotropic plasma etching of the exposed areas of polycrystalline layer 22 is performed, inside of openings 25 and 26 . For this purpose, a gaseous mixture comprising chlorine and helium is used. Tip fields 28 and 29 are then obtained in each of openings 25 and 26 in the upper portion of polycrystalline layer 22 .
[0046] In the case of a polycrystalline layer 22 formed of silicon, and of a protective layer 23 formed of silicon oxide, it is possible to obtain tips with a height on the order of 10 μm by performing an anisotropic plasma etching exhibiting the following characteristics. The chlorine gas flow rate is 130 cm 3 per minute and the helium gas flow rate is 70 cm 3 per minute. The gas pressure is 4,000 mT. The etch time ranges between 10 and 20 minutes. The power used for a device of type LAM 490 is 300 watts, the distance between electrodes being 0.5 cm.
[0047] Although two openings 25 and 26 are shown in FIG. 4D , the device formed according to the above-mentioned method may comprise a multitude of openings, for example, arranged in a matrix. Such a device enables placing in the openings various types of biological cells or various types of elements to be introduced into the cells by transfection. This enables performing various types of analyses.
[0048] Another example of embodiment of the present invention is described hereafter in relation with FIGS. 5A to 5D .
[0049] In an initial step, shown in FIG. 5A , an etch mask is deposited on a structure such as that illustrated in FIG. 4B and comprising a stacking of a substrate 20 , of an insulating layer 21 , and of a polycrystalline layer 22 . The etch mask comprises an assembly of protective blocks 30 and 31 placed on polycrystalline layer 22 .
[0050] At the next step, illustrated in FIG. 5B , an anisotropic etching of polycrystalline layer 22 is performed according to a standard method providing polycrystalline blocks 40 and 41 placed under protective blocks 30 and 31 . The etch mask, that is, protective blocks 30 and 31 , is then removed.
[0051] At the next step, illustrated in FIG. 5C , an anisotropic plasma etching of polycrystalline blocks 40 and 41 is performed by using a chlorine and helium gas mixture. Tip fields 50 and 51 formed in the upper portion of polycrystalline blocks 40 and 41 are then obtained.
[0052] At the next step, illustrated in FIG. 5D , a thin conductive layer, for example, made of gold, is deposited over then entire previously-described structure. This thin conductive layer is then etched to be eliminated between polycrystalline blocks 40 and 41 except at certain previously-defined locations to form conductive tracks 60 and 61 on insulating layer 21 . Polycrystalline blocks 40 , 41 and tip fields 50 , 51 are then covered with conductive films 65 , 66 connected to conductive tracks 60 , 61 . Conductive tracks 60 and 61 connect conductive films 65 , 66 covering tip fields 50 and 51 to contact terminals placed, for example, at the periphery of substrate 20 .
[0053] Although two polycrystalline blocks 40 and 41 are shown in FIG. 5D , the device formed according to the above-mentioned method may comprise a multitude of polysilicon blocks arranged, for example, in a matrix. Many contact terminals are then provided and placed, for example, at the wafer periphery. These contact terminals are connected to the tip fields formed at the surface of the polycrystalline blocks by means of multiple conductive tracks placed on insulating layer 21 .
[0054] An example of use of such a device is the following. The contact terminals are electrically connected to a measurement device. This enables evaluating the activity of biological cells placed on the tip fields by measuring, for example, values of potentials or electric currents.
[0055] The surface of the polycrystalline blocks of the device may be of a size identical to or lower than that of a biological cell. The device thus obtained enables analyzing a “tissue” of biological cells, such as a piece of skin, by placing this device against the tissue. It is then possible to analyze the activity of the various cells in the tissue. The activity of cells such as neurons of a neural network may, for example, be analyzed.
[0056] Of course, the present invention is likely to have various alterations, modifications, and improvements which will readily occur to those skilled in the art. In particular, those skilled in the art may devise other forms of device that can be obtained according to the method of the present invention.
[0057] Such alterations, modifications, and improvements are intended to be part of this disclosure, and are intended to be within the spirit and the scope of the present invention. Accordingly, the foregoing description is by way of example only and is not intended to be limiting. The present invention is limited only as defined in the following claims and the equivalents thereto. | A method for manufacturing a device including a field of micrometric tips, including forming a polycrystalline layer on a support; performing an anisotropic plasma etching of all or part of the polycrystalline layer by using a gas mixture including chlorine and helium, whereby tips are formed at the surface of the polycrystalline layer. | 1 |
BACKGROUND OF THE INVENTION
The present invention relates to steam irons in which steam is produced in a quasi-instantaneous manner. These appliances have a useful life that is limited by the build up of scale in the steam chamber.
Numerous devices for reducing the occurrence of scale in an iron have been proposed. One of the most successful physical-chemical systems diffuses a phosphorated product into water before the water is vaporized in order to impede crystallization of the scale in a hard form and to permit its removal by the steam flow. French patent FR 2 757 364 describes an embodiment of such a device where the diffusion of sodium hexametaphosphate (SHMP), which is highly soluble, is controlled by a silicone matrix placed in the water circuit. However, it has been noted that the scale that is formed tends to partially agglomerate under the action of the steam and detaches in the form of flakes that are friable but that are evacuated in bunches that stain the fabric being ironed.
The particles can be retained in the steam chamber by a metal screen as suggested in the German patent DE 3006783 or the Japanese patent 60160999. A screening can equally be produced in a manner disclosed in the French patent FR 2 696 197 where a grid intended to improve the vaporization has its edges raised in the form of bowl. However, the utilization of a screening grid alone eventually provokes blockages of the steam chamber by very hard scale, which cannot be evacuated.
BRIEF SUMMARY OF THE INVENTION
The present invention has as an object a scale reducing device that will prolong the useful life of a steam iron while permitting regular evacuation of scale in a powder form powder that is invisible to the user and will not stain articles being ironed, while preventing obstruction of the chamber as well as of the steam vaporization channels, including the steam delivery holes in the iron soleplate.
The above and other objects are achieved, according to the invention, by a steam iron composed of: a metal heating body containing a chamber that has a steam generating zone; means defining a water flow path in communication with the chamber, the water flow path including a compartment containing a quantity of a scale reducing agent that is contacted by water flowing along the path before the water reaches the chamber, the scale reducing agent being obtained by cross-linking or hardening a silicone elastomer of an organosilicic system that is permeable to water vapor and having an active hydrophilic material and a polyorganosiloxane composition; and a screen made of a metal different from that of the heating body and disposed in proximity to the steam generating zone at a location to be traversed by steam generated in the steam generating zone.
The scale reducing agent could be fabricated in the manner disclosed in French patent FR 2 757 364.
Preferably, the active hydrophilic material is selected from among the metaphosphates of sodium or of potassium. It has been found that in the case of steam irons according to the present invention, no visible flakes exit through the steam delivery holes of the soleplate even when the screen has holes with a hydraulic diameter of the order of two millimeters. Surprisingly, scale does not accumulate in the steam chamber, or in the steam flow channels.
Preferably, the screen is fitted, or gripped, or clamped, tightly between two walls of the steam chamber of the pressing iron.
The process that permits the scale to be present in the form of a very fine powder that is not visible at the outlet of the iron is not clearly understood. Possibly, the friable flakes that detach from the steam generating zone are retained and rub against the screen, which breaks them into the very fine particles. Possibly, the scale that is deposited on or against the screen is broken up by thermal expansion and contraction of the screen. It is also possible that there is an unknown phenomenon resulting from the difference in electrical potential caused by the different characteristics of the metal making up the heating body and the different metal of the screen. This difference in electric potential could have an effect due to the good electric connection resulting from the tight gripping of the screen in the heating body.
Preferably, the screen is coated with a gold layer. This layer protects the screen and prevents it from rusting or corroding. It is also noted that the gold gives rise to a large electric potential difference with a heating body made of aluminum. According to another possibility, the screen can be made of stainless steal.
In either case, the screen is protected from oxidation phenomena and the appearance of a potential difference with a heating body of aluminum is promoted.
Also preferably, the screen is made of an expanded metal that is better able to break up the scale which comes to deposited on or against the screen.
Preferably, the scale reducing agent is contained in a tube and librates its active ingredients through at least one open end of the tube.
The silicone can be in form of matrix molded into the tube without requiring another mold. The active material is librated with a kinetic of the order of unity. This means that the active material is librated at a substantially rate, at least when the temperature of the matrix remains substantially constant. The active material is librated through a progressive front of cracks in the matrix, which coincides with the cross section of the tube so that the liberation of active material is thus perfectly controlled.
Preferably, the tube containing the scale reducing agent is placed in the water reservoir of the iron. The scale reducing agent can be present in a quantity sufficient to assure a good functioning of the system during the entire expected useful life of the iron, or can be renewable. Placement in the water reservoir is simplified when the matrix is molded within the tube.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a simplified side cross-sectional view, along line I—I of FIG. 2, of a pressing iron constructed according to the present invention.
FIG. 2 is a plan view of the soleplate of the iron shown in FIG. 1 .
DETAILED DESCRIPTION OF THE INVENTION
A preferred embodiment of a steam pressing iron according to the invention is shown in FIGS. 1 and 2. This iron is composed of a soleplate 1 having a steam generating chamber 2 , a water reservoir 3 , a droplet delivery system 4 permitting water to be supplied at a desired rate to chamber 2 from reservoir 3 , and a housing, or casing, 5 that includes a handle for grasping the iron.
Reservoir 3 is formed by two pieces 300 and 301 and has a filling opening 302 that can be closed by a sliding cover 303 . A tubular element 304 having a constant cross-section perpendicular to the plane of FIG. 1 is disposed at the interior of reservoir 3 . Element 304 is filled with a molded silicone elastomer matrix 305 containing SHMP in the form of a solid dispersion. One or both ends of element 304 , which ends are parallel to the plane of FIG. 1, are open to expose matrix 305 to water within reservoir 3 . Element 304 is installed to be in contact with water in reservoir 3 .
Soleplate 1 contains a heating body 100 made of aluminum and defining the walls of steam generating chamber 2 . Soleplate 1 further has a tubular resistive heating element 101 , a closing plate 102 and a cap, or liner, 103 that is in thermal communication with heating body 100 . Closing plate 102 constitutes the upper wall, or cover, of chamber 2 . Liner 103 constitutes the external ironing surface of the iron and is intended to be in contact with articles that are being ironed.
Chamber 2 has a zone 200 , shown most clearly in FIG. 2, into which water drops are delivered from system 4 . Zone 200 , in which steam is produced, is extended across soleplate 1 by a second zone 201 that is closed by ribs 202 and a screen 203 . Screen 203 is an element preferably made of an expanded metal, such as stainless steel, optionally plated with a thin layer of gold. Screen 203 is tightly clamped between closing plate 102 and the bottom of chamber 2 in order to assure an excellent electric contact between plate 102 , screen 203 and heating body 100 . An electric potential difference is established between screen 203 and heating body 100 as a consequence of the different characteristics of the two different metals employed for screen 203 and heating body 100 .
Screen 203 is formed to have a mesh width between 0.3 and 3 millimeters and is made up of wires preferably having a polygonal cross-section, which may for example be triangular, square, or rectangular. Screen 203 is made of a metal material different from that of heating body 100 and/or plate 102 , and may for example be made of stainless steel, optionally covered with a gold layer having a thickness between 10 μm and 100 mμ.
Advantageously, the bottom of chamber 2 is covered with an anti-calefaction coating, i.e. a coating that prevents water droplets dropped onto a hot plate from remaining in liquid form. The steam produced in chamber 2 can escape through passages 206 , channels 204 and holes 207 toward steam delivery openings 205 that are provide in liner 103 for delivery to an article being pressed, either directly or via other distribution channels located the soleplate. The steam delivery passages and channels and the steam outlet openings in liner 103 can be formed according to principles that are well known in the art.
When the pressing iron is at room temperature, only very little SHMP is librated from silicone matrix 305 , even if matrix 305 is wetted. When the iron is to be used, the user fills water reservoir 3 via opening 302 and then moves cover 303 into the closed position shown in FIG. 1 . When the iron is heated, the temperature in the reservoir is first raised to a moderate level that is sufficient to strongly accelerate diffusion of SHMP into the water, and vapor diffusing toward the SHMP grains, which are very hydrophilic, causes the grains to be charged with water and to swell, thereby breaking the silicone network. The SHMP diffusion front progresses slowly into the matrix along the axis of tubular element 304 , i.e. perpendicular to the plane of FIG. 1, the cross-section of element 304 being constant in this direction, and the diffusion of SHMP is thus well controlled.
Preferably, the length and cross-section of tubular element 304 are selected to assure a continued diffusion of the scale-preventing product for the useful life of the iron. In another form of construction, tubular element 304 and its silicone matrix 305 are replaceable.
During ironing, the user can activate a control element 40 to operate system 4 , leading to the production of steam that will be used in the ironing process. When control element, or button, 40 is depressed, water containing dissolved SHMP is allowed to flow in the form of drops from reservoir 3 into chamber 2 , where the drops fall into zone 200 . The water spreads out to a greater or lesser extent across chamber 2 , the extent depending on the flow rate, and reaches zone 201 . Vaporization of the water produces steam which flows toward the article being ironed while passing through screen 203 and then into passages 206 and channels such as 204 and holes 207 in order to reach delivery of openings 205 of the soleplate.
Any scale left by the vaporization of the water is in large measure in powder form due the action of the SHMP and is evacuated by being at least in part entrained by the steam.
Another part of the scale left by the water attaches to the wall of chamber 2 in the form of a crumbly, or friable, layer, which scale material subsequently detaches in the form of flakes that are then retained by screen 203 . A further part of the scale comes to be deposited as a crust directly on screen 203 . Surprisingly, the flakes and the crust of scale disintegrate at the level of the screen into a fine powder that is invisible to the naked eye, this powder then being evacuated out of the iron through the steam delivery openings. It is thought that the electric potential differential present at the level of screen 203 , of the order 2-3 volts, provokes a transformation of the cohesion of the scale crystals, this transformation possibly being completed by the polygonal geometry of the cross-section of the wires of the screen. Screen 203 then is able to prevent the passage of large particles and retains them so that they can be transformed into fine powder. According to other embodiments of the invention, the SHMP can be replaced another hydrophilic phosphorous product.
As a result, the scale is evacuated regularly in an invisible form and without inconveniencing the user. The useful life of the iron is increased by the hydrophilic scale-preventing product while, at the same time, this product does not create any inconveniences, such as the appearance of stains on the articles being ironed.
This application relates to subject matter disclosed in German Application No. DE-100 14 815.8, filed Mar. 27, 2000, the entirety of which is incorporated herein by reference.
The foregoing description of the specific embodiments will so fully reveal the general nature of the invention that others can, by applying current knowledge, readily modify and/or adapt for various applications such specific embodiments without undue experimentation and without departing from the generic concept, and, therefore, such adaptations and modifications should and are intended to be comprehended within the meaning and range of equivalents of the disclosed embodiments. It is to be understood that the phraseology or terminology employed herein is for the purpose of description and not of limitation. The means, materials, and steps for carrying out various disclosed functions may take a variety of alternative forms without departing from the invention. Thus the expressions “means to . . . ” and “means for . . . ”, or any method step language, as may be found in the specification above and/or in the claims below, followed by a functional statement, are intended to define and cover whatever structural, physical, chemical or electrical element or structure, or whatever method step, which may now or in the future exist which carries out the recited function, whether or not precisely equivalent to the embodiment or embodiments disclosed in the specification above, i.e., other means or steps for carrying out the same functions can be used; and it is intended that such expressions be given their broadest interpretation. | A steam iron composed of: a metal heating body containing a chamber that has a steam generating zone; a water flow path in communication with the chamber, the water flow path including a compartment containing a quantity of a scale reducing agent that is contacted by water flowing along the path before the water reaches the chamber; and a screen made of a metal different from that of the heating body and disposed in proximity to the steam generating zone at a location to be traversed by steam generated in the steam generating zone. | 3 |
RELATED APPLICATION
This application is related to and claims the benefit of priority from German Patent Application No. 102 49 550.5, filed on Oct. 23, 2002, the entirety of which is incorporated herein by reference
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a superconducting cable conductor with a superconducting material based on rare earth barium cuprates, the superconductor material being applied in layer form on a tape-type substrate. In particular, the invention relates to a superconducting cable conductor of this type for AC applications.
2. Description of the Prior Art
Superconducting cable conductors are usually constructed from a generally cylindrical carrying element with superconducting wires wound helically thereon as superconducting conductor elements.
The carrying element may comprise a conductive or nonconductive material and is usually configured in flexible fashion.
The superconducting conductor elements are wound 20 helically on said carrying element in one or more layers. Each individual layer is obtained by a plurality of, for example tape-type, superconducting conductor elements being wound next to one another onto the carrying element or onto a layer that has already been wound onto the carrier element.
Thus, EP 0 650 205 52 describes a multilayered superconducting cable conductor for AC applications, multifilament wires being used as conductor elements.
The multifilament wires contain a multiplicity of 30 filament-type cores comprising a superconductor material which are embedded in a matrix comprising a normally conducting metal, in particular silver. In order to avoid AC losses on account of eddy currents and coupling currents, insulating layers comprising an insulating material are provided between the individual layers comprising superconducting wires.
The superconducting wires are obtained by filling for example pulverulent starting material, which can be converted into the desired superconductor material by means of suitable thermal treatment, into a casing comprising a normally conducting metal, preferably silver. The casing filled with the pulverulent starting material is subjected to a plastic deformation with drawing and rolling to form a long filament having a small diameter and is subsequently sintered. The individual filaments obtained are combined to form a bundle comprising a multiplicity of individual filaments and passed together into a further casing, which is in turn subjected to a plastic deformation and sintering. A superconducting multifilament wire with the desired number of filaments in a metal matrix is obtained as a result. The finished multifilament wire preferably has a tape form.
The superconductor material acquires the desired 20 high orientation as a result of the treatment described above, the crystallographic c axis essentially extending perpendicular to the current flow direction and the a-b plane extending parallel to the current flow direction. The orientation should preferably be as homogeneous as possible over the entire extent of the superconducting material.
Depending on the diameter of the carrying element onto which the multifilament wire is wound, and on the lay length of the individual turns, forces as a result of bending elongation and tensile stress are exerted on the wires during the winding process and in the unwound state. This may result in an impairment of the orientation of the superconducting phase and thus in a reduction of the superconducting properties.
In order to be able to obtain the greatest possible freedom with regard to the diameter of the carrying element and the lay length of the winding and thus with regard to the cable construction, a superconducting cable is desirable, therefore, in which no degradation of the superconducting wires occurs even in the case of a relatively high degree of bending for example in the case of a small diameter of the carrying element and/or a small lay length, and relatively high tension.
SUMMARY OF THE INVENTION
According to the invention, this object is achieved by means of a superconducting cable conductor which contains a carrying element, onto which is wound at least one layer comprising two or more superconducting conductor elements, the individual superconducting conductor elements of each layer being arranged next to one another, and the superconducting conductor elements contain a tape-type substrate coated with a semiconducting material based on rare earth barium cuprate.
Hereinafter, the superconducting conductor elements used according to the invention, comprising a tape-type substrate coated with a superconducting material based on rare earth barium cuprate, are also called “REBCO-coated conductor elements”, where RE=one or more rare earth elements including lanthanum and yttrium, or “coated conductor elements”.
As in the case of the superconducting multifilament wires described in the introduction, here too the quality of the superconducting properties depends on the extent of the orientation of the superconducting crystals in the layer. In order to achieve a high critical current, high current density and current-carrying capacity, it is advantageous, therefore, if the superconducting material in the coated conductor element has the highest possible biaxial orientation (texturing), the crystallographic c axes of the individual superconducting crystals being arranged perpendicular or essentially perpendicular to the surface of the tape-type substrate and the a-b planes being arranged parallel or essentially parallel to the surface of the tape-type substrate, so that the a-b planes extend in the current flow direction.
Coated conductor elements as are used according to the invention, methods for producing them, precursor materials suitable therefor for forming the superconducting material and suitable substrates are generally known to persons skilled in the art and described in numerous instances in the literature. By way of example, reference is made in this respect to N. McN Alford et al., “Topical review: High-temperature superconducting thick films” in Supercond. Sd. Technol. (1997) 169–185, J. L. MacManus-Driscoll “Recent developments in conductor processing of high irreversibility field superconductors” in Annu. Rev. Mater, Sd. volume 28 (1998) pages 421 to 462 and WO 98/58415.
In this case, the desired texturing of the superconducting layers is achieved by using specific substrates, the properties of the substrate, in particular the texture thereof, bringing about the orientation of the crystals growing in the superconducting layer.
Suitable methods and materials for producing coated conductor elements as may be used according to the invention, a layer comprising superconducting material being deposited on a substrate, are, for example, the ion beam assisted deposition (IEAD) or assisted biaxially textured substrates (RABiTS) methods as are described for example in Y. Jijima et al., “In-plane aligned YBCO thin films deposited on polycrystalline metal substrates”, in Appl. Phys. Lett. 60 (1992) page 769 for IEAD and A. Goyal et al. “Fabrication of long range, biaxially textured, high Tc superconducting tapes˜˜in Appl. Phys. Lett. 69 (1996), page 1795 for RABiTS.
Further suitable deposition methods are pulsed laser deposition (PLD) as described for example in A. Usoskin et al., EUCAS 99, page 447 and by S. R. Foltyn et al., in IEEE Trans. on Applied Supercond., 9, (1999), page 1519, and the solution-assisted (sol-gel) method as described for example by M. P. Siegel et al., in Appl. Phys. Lett., volume 80, No. 15 (2002) pages 2710 to 2712. A further suitable method is the so-called BaF 2 method, as described for example by S. W. Lu et al. in Supercond. Sci. Technol., 14 (2001) pages 218 to 223, fluorine in the form of BaF 2 being added to the starting material for the formation of the superconductor material.
The substrate used for the coated conductor element that is to be used according to the invention may be any desired substrate provided that it neither adversely affects the superconductor material of the layer nor is impaired by the processing processes for forming the superconducting layer. Examples of substrates are monocrystalline ceramics, polycrystalline ceramics or metals.
The cross-sectional form of the tape-type substrate 25 may be selected as desired, in principle. The cross section may be in, for example, rectangular, square, oval, round, polygonal, trapezoidal, etc. form. An essentially rectangular form is generally preferred, however.
It goes without saying that substrates with a sufficient flexibility for the desired cable application are to be used for the superconducting conductor elements that are to be used according to the invention.
One or more thin intermediate layers may be 35 provided as buffer layer between the superconducting layer and the substrate.
The buffer layer prevents the substrate material from reacting with the superconducting material in an undesirable manner.
Thus, for example when using metals as substrates, a suitable buffer layer comprising a ceramic should be provided.
Examples of suitable materials for the buffer layer are zirconium oxide, stabilized zirconium oxide such as, for example, zirconium oxide stabilized with yttrium oxide (YSZ), CeO 2 and MgO, but also SrTiO 3 , LaAlO 3 .
A superconducting oxidic material based on rare earth barium cuprates is used as superconducting material for the present invention. The rare earth barium cuprates contain at least one rare earth element (RE) selected from among Y, La, Ce, Pr, Nd, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, preferably yttrium or yttrium in combination with at least one further rare earth element.
Particularly preferred compounds have the general 20 formula
SEBa 2 Cu 3 O 7−X , where x≦0.5.
In addition, the rare earth barium cuprates may contain at least one further element selected from the group consisting of Be, Mg, Ca, Sr, Zn, Cd, Sc, Zr, Hf, Pt, Pd, Os, Ir, Ru, Ag, Au, Hg, Ti, Pb, Bi, Ti, S and F.
Particular preference is attached to YBa 2 Cu 3 O 7−X where x≦0.5 (also called Y1, 2, 3), which may additionally contain at least one further rare earth element and/or at least one further element from the group of elements mentioned above.
For production purposes, the starting materials for the superconducting material, for example according to one of the methods mentioned above, are deposited on the substrate, which is optionally provided with a buffer layer, and are subjected to a thermal treatment with controlled fusion and cooling to form the desired superconducting 123 phase.
It is known that the 123 material can be obtained from a material of the composition Se 2 BaCuO, the so-called 211 material, by controlled fusion and cooling.
In accordance with a preferred method, the texturing is effected by making use of the different peritectic solidification temperature of 123 materials with different rare earth elements.
For this purpose, at least two 211 materials which differ in terms of the RE component are arranged in strip form along the longitudinal direction on a tape-type substrate, the mutually adjoining longitudinal edges of the strips of 211 material being in contact.
A corresponding layer comprising barium cuprate and/or copper oxide is applied on the strips comprising the two different 211 materials for the purpose of setting the stoichiometry of the 123 material to be formed, which layer at least partially covers the strips. Since the barium cuprate and/or copper oxide has a lower melting point than the 211 materials, it is the first to melt during a subsequent thermal treatment. The melt that is formed infiltrates the underlying starting materials, the latter at least partially dissolving in the melt. The desired 123 material forms during cooling from this partial melt with the barium cuprate/copper oxide as liquid phase with dissolved solid 211 material.
At the same time, the rare earth elements migrate on account of diffusion and melting processes, concentration gradients for the respective rare earth elements of the starting materials forming in the opposite direction transversely with respect to the strip.
During slow isothermal cooling, the solidification 35 front advances from the side with the 123 material having the highest solidification temperature to the side with the 123 material having the lowest solidification temperature, a biaxial orientation of the crystals that form being effected.
Preferably, a strip comprising a 123 material is arranged as initiator on the side on which the 123 material having the higher solidification temperature forms, the rare earth element for said 123 material being chosen such that the solidification temperature of the 123 material is higher than the solidification temperature of the 123 materials that form.
In this case, this rare earth element also forms a concentrating gradient in the direction of the 211 starting material arranged on the opposite side.
A suitable material combination comprises an arrangement of Nd123, Y211 and Yb211 in this order, the following holding true for the peritectic solidification temperatures Tp: Tp Nd123>Tp Y123>Tp Yb123. According to this method, it is possible to obtain 20 biaxially textured layers having a thickness of 1 .mu.m, and in particular 5 .mu.m or more, an excellent biaxial orientation being possible even without corresponding preorientation of the substrates. Therefore, it is not necessary to use substrates which contain a lattice matching to the biaxial texturing to be formed.
A further embodiment for the above-described method for producing in particular biaxially textured superconducting layers, the texturing being effected independently of the substrate, is described in DE 101 28 320 C1, to the entire contents of which reference is made here. Here, too, a concentration gradient, and thus a temperature gradient, is formed by the addition of further rare earth elements.
Above-described methods making use of temperature gradients make ±t possible to obtain polycrystalline layers with large biaxially oriented crystals through to monocrystalline layers. The misorientation of the crystals in the layer is preferably not more than 7°.
Layers of this type are particularly preferred for 5 superconducting applications.
The core of the superconducting cable conductor according to the invention is formed by the carrying element. In principle, the carrying elements that are known per se for the production of superconducting cable conductors can be used for the present invention. Usually, the carrying element used according to the invention is essentially cylindrical.
The carrying element may be formed as a tube or as a solid core element.
If it is formed as a tube, the cavity in the interior of the tube may be used as a channel for the cooling medium. The cooling medium flows through the cavity and in the process transports away the heat loss arising during the use of the superconducting cable.
The carrying element may generally be formed from a metal or plastic and usually has a low electrical conductivity.
Provided that the required flexibility is given, it is also possible to use any other suitable material desired.
In accordance with a particular embodiment, however, the carrying element may be formed as a solid core element comprising an electrical conductor. In this case, in the event of a short circuit, when the superconducting layer undergoes transition to the normally conducting state, the electrically conductive core element can carry the current and damage to the superconducting layer can thus be avoided.
It is essential for the carrying element to be flexible. This can be achieved by the carrying element having an annular or spiral corrugation. In this case, the individual waves are arranged along the longitudinal extent of the carrying element parallel in the case of the annular corrugation, and obliquely in the case of the spiral corrugation, with respect to the cross section of the carrying element. However, the carrying element may also be formed as a helix.
The carrying element may have, as required, an armoring comprising a metal or plastic braiding, for example comprising a high-grade steel braiding.
The carrying element may furthermore have a taping comprising metal or plastic tapes, for example a high-grade steel tape, which are wound helically next to one another onto the carrying element. This may result in a mechanical reinforcement of the carrying element. At the same time, the armoring or the taping serves to form a smooth surface as a support for the coated conductor elements.
If the armoring comprises a metallically conductive 20 material, it may likewise serve to take up short-circuit currents.
A padding may be provided, as required. For this purpose, one or more layers of semiconductive or insulating tape may be applied to the carrying element, said layers being wound helically onto the carrying element with or without an overlap.
In order to form the individual layers, a plurality of coated conductor elements are wound helically next to one another onto the carrying element or onto a corresponding underlying layer comprising coated conductor elements.
The individual layers may be wound onto the carrying element in the same sense or in opposite senses.
In addition, all of the layers or individual layers 35 may have different lay lengths or angles for the winding. It is possible to achieve a uniform current distribution over the individual layers through the selection of the winding direction and/or the angles of the winding. This is of importance for applications with alternating current since here, in the absence of corresponding measures, a nonuniform current distribution may occur over the individual layers, with a different quantity of current flowing in the individual layers.
If a very high current flows in one layer, for 10 example, there is the risk of the critical limit value being exceeded.
Since the coated conductor elements with a superconducting layer based on rare earth barium cuprate that are used according to the invention can withstand even a relatively high bending elongation and a relatively large tension without degradation and thus impairment of the orientation of the superconducting material, superconducting cables which may have a carrying element having a low diameter may be obtained according to the invention.
On account of the possible low diameter of the carrying element, given comparable superconducting properties it is possible to obtain thinner cables or, given a comparable thickness to conventional cables based on multifilament wires, the cables according to the invention have a higher superconducting cross section.
The lay length may also be chosen to be variable to a greater extent.
The greater degrees of freedom that become possible 30 as a result of this in the configuration of the cable mean that the cable, as required, may be configured as exactly as possible for the respective application. It is particularly advantageous that overall thinner cables can be obtained which nevertheless have sufficient superconducting properties.
Moreover, a greater range of variation for the angles for the winding becomes possible, so that an optimum coordination of the angles for the individual layers is possible for achieving a uniform current distribution over the layers.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The text below specifies concrete examples for the configuration of a superconducting cable conductor according to the invention and for superconducting conductor elements that can be used therefor, of the kind that may usually be used. It goes without saying that, as required and depending on the application, deviations from the details that are mentioned here merely by way of example are possible and concomitantly encompassed by the invention. Construction of the superconducting conductor elements
Thickness of the substrate: approximately 0.025 mm to approximately 2 mm
Width of the substrate: approximately 10 mm
Thickness of the superconducting layer: approximately 1 μm to 5 μm
Buffer layer: approximately 1 μm
If the substrate comprises nickel or an Ni alloy, for example, ZSY is preferably used as the buffer layer.
The number of superconducting conductor elements per layer generally depends on the external diameter of the carrying element and the tape width. Thus, by way of example, for a carrying element having a diameter of 25 mm, it is possible to use 7 conductor elements as described above per layer, and with 30 mm it is possible to use 9 tapes per layer. 4 to 6 is a customary number of layers.
In a cable conductor with 4 layers, in order to achieve a uniform current distribution, layers 1 and 2 may be wound in the same sense but at different angles and layers 3 and 4 may be wound in the opposite sense thereto, likewise at different angles.
With a cable conductor according to the invention for example with a configuration as described above, it is possible to obtain current densities of 1 000 000 to 3 000 000 A/cm 2 .
In order to avoid electrical interactions between the individual layers comprising coated conductor elements, an electrically insulating layer may be provided between each layer or after a specific number of layers.
Said electrically insulating layer may be formed from a film or a tape comprising an insulating material. A tape may likewise be wound helically onto the corresponding layer comprising coated conductor elements in a manner known per se.
An electrically insulating layer may be provided, as required, between the carrying element and the first layer comprising superconducting conductor elements. Suitable materials for said electrically insulating layer are the same as those mentioned above for the insulating layers which are arranged between the individual layers comprising superconducting conductor elements.
Individual conductor elements of a layer, groups of 25 a plurality of conductor elements of a layer or all the conductor elements of a layer may also be electrically insulated from one another.
For this purpose, an insulating material may be provided between the corresponding conductor elements.
By way of example, a tape comprising an insulating material may be wound parallel to the conductor elements of a layer, so that the tape runs between the individual conductor element strands and isolates the latter from one another.
Any suitable electrically insulating material may be used per se as material for the electrical insulation between the individual layers, between carrying element and superconducting winding and between the conductor elements of a layer.
Examples are plastics, paper or plastic-laminated paper and also other materials known therefor. The insulations described above, i.e. between the superconducting layers, layer and carrying element and between the conductor elements of a layer, may also be used in combination with one another.
An example of the production of a preferred coated conductor element is given below. In this case, the production is explained by way of example using a piece of tape comprising AgPd 12.5 (palladium in percent by weight) as substrate having a length of approximately 5 cm, a thickness of approximately 100 μm and a width of approximately 2 cm. It goes without saying, however, that the method can also be applied to substrates having different dimensions from those mentioned by way of example above.
The starting materials were present as a powder with an average particle diameter in the range of from 1 to 50 μm.
Brushes or an airbrush were used to arrange on the 25 carrier material next to one another a 1 mm wide line comprising Nd123 (1) (5 cm long, overall about 40 mg Nd123), a 5 mm wide line comprising Y211 (2) (5 cm long, overall about 200 mg Y211) and a two millimeter wide line comprising Yb211(3) (5 cm long, overall about 90 mg) next to one another such that adjacent longitudinal edges were in contact with one another. The resulting strip was covered with a layer comprising overall 400 mg of Ba 2 C 3 O 5 .
The carrier material thus coated was placed in air 35 in a commercially available chamber furnace comprising an Al 2 O 3 block and subjected to the following thermal treatment.
Start Temperature
Heating Rate
Target Temperature
Hold Time
Room temperature
500° C./h
500° C.
2 h
500° C.
500° C./h
975° C.
1 h
975° C.
0.5–1° C./h
950° C.
0 min
950° C.
100° C./h
Room Temperature
During the first step of this thermal treatment, primarily the solvents used, water with 2% by weight of polyvinyl alcohol (PVA), were evaporated.
During the second step of the thermal treatment, the mixture comprising silver, barium cuprate and copper oxide—the liquid phase—fused and formed a doped barium cuprate melt which infiltrated the underlying starting materials arranged next to one another. The starting materials (1), (2) and (3) were at least partially dissolved by this liquid phase. A concentration gradient of neodymium formed, which extended from starting material (1) proceeding in the direction of starting material (3). Conversely, a concentration gradient of ytterbium additionally formed, which extended from starting material (3) proceeding in the direction of starting material (1).
On account of the different peritectic solidification temperatures Tp for different superconductors (RE)Ba 2 Cu 3 O 7 -X where Tp (Nd123)>Tp (Y123)>Tp (Yb123), a gradient of the solidification 25 temperature resulted in the overall system on account of the concentration gradient mentioned above. During the spatially isothermal, slow cooling in step 3, this promoted a directional growth of the superconductor crystals parallel to the gradient of the solidification temperature.
In order to produce the superconductivity, the samples obtained were heated to 500° C. for 50 to 100 hours in an atmosphere with an oxygen partial pressure of 1 bar. In this method step, the oxygen content of the samples was optimized to the effect of x in YBa 2 Cu 3 O 7−X becoming minimal but always less than 0.5. The heating and cooling rates of the oxygen treatment were about 100° C./h.
The thicknesses of the thick layers obtained were typically in the range of between 10 and 15 μm. | The present invention relates to a superconducting cable conductor which contains a carrying element, on which is wound at least one layer comprising two or more superconducting conductor elements, the individual conductor elements of each layer being arranged next to one another, and the superconducting conducting elements are formed from a tape-type substrate coated with a superconducting material based on rare earth barium cuprate, preferably based on yttrium barium cuprates. | 8 |
BACKGROUND OF THE INVENTION
The present disclosure relates generally to the analysis of automatic line insulation testing data and in particular, to a method of facilitating the retrieval, organization and analysis of automatic line insulation testing data.
A typical regional telephone company central office, or wire center, houses a telephone switch to connect telephone calls between two or more parties. A main distribution frame (MDF) frame includes a row of jumpers to connect the switch wires to cable pairs from outside of the central office. Some cables utilize paper as insulation between the wires in the cable. Air compressors, located in the central office, are utilized to minimize the amount of water in the cables. When a cable gets nicked, the paper inside the cable may get wet and cause a short in the cable. It may be necessary to deploy a technician to fix the cable depending on factors such as the number of shorts in a particular cable. In some cases, such as when there is only one short in the cable, the paper may be dry once the technician gets to the cable to repair it. Sending a technician to repair a problem that was corrected should be avoided and technicians should be sent to repair cables that need technician action. One way to determine if a repair package should be built to send a technician to correct a problem is to have criteria such as: only build a repair package if there are more than three shorts, or crossings, of more than twenty volts in a twenty-five pair complement; and if there is only a two volt cross in a cable pair then do not build a repair package as the paper within the cable will probably be dry once the technician gets there. Any criteria may be used to determine when to build a repair package and the criteria may be varied or modified based on experience (e.g., in general or in a particular geographic location).
Currently, many regional telephone companies utilized an off-the-shelf computer product called Predictor to compile morning reports detailing automatic line insulation testing (ALIT) exceptions. ALIT is performed nightly by equipment that sequentially tests lines in the central office for battery crosses and grounds. The Predictor reports that include the results of all the tests, including good cables and cables with battery crosses and grounds, are sent to a printer. The Predictor report for each state (e.g., Tennessee) requires about one box of paper each night. Each morning maintenance administrators (MAs) analyze the reports and build Predictor patterns so that the technicians in the field may correct the problems identified by the tests. The MAs must sift through a box or more of paper each morning to find the failures, or exceptions, that need to be fixed. This practice may be cumbersome for the MA and because it is manual, may be error prone. Also, it may take all morning for the MA to sort through a particular portion of the Predictor report, with repair packages not being built until the afternoon. In addition, the current process does not produce back-up information for determining what information was presented to the MA when a decision to build a repair package was made.
BRIEF DESCRIPTION OF THE INVENTION
One aspect of the present invention is a method for analyzing automatic line insulation testing data. The method comprises receiving an electronic version of ALIT test results and parsing the ALIT test results to extract error data. The error data is inserted into an ALIT database. The ALIT database includes one record for each exception located in the error data and each record includes: a wire center attribute, an exception date attribute, a facility number attribute, a cable attribute, a pair attribute, a repair package attribute, a maintenance analyst name attribute, a trouble message attribute, a telephone number attribute, a tea attribute and a test result attribute. The number of exceptions per wire center occurring on a selected summary date is calculated in response to receiving a summary request from a user. The summary request includes the selected summary date and input to the calculating is the selected summary date and the ALIT database. The number of exceptions per wire center occurring on the summary date is transmitted to the user in response to the calculating. User records located in the ALIT database that include a selected wire center and a selected detail date are transmitted to the user in response to receiving from the user a wire center detail request. The wire center detail request includes the selected wire center and the selected detail date. The ALIT database is updated with repair package information in response to receiving an add repair package request. The add repair package request includes a wire center, a facility, a cable, an exception date, a repair package number, a low pair and a high pair.
In another aspect, a system for analyzing automatic line insulation testing data comprises a network and a storage device in communication with the network. The storage device includes an ALIT database. The system further comprises a user system in communication with the network and a host system in communication with the network. The host system includes application software to implement a method comprising receiving an electronic version of ALIT test results via the network and parsing the ALIT test results to extract error data. The error data is inserted into an ALIT database. The ALIT database includes one record for each exception located in the error data and each record includes: a wire center attribute, an exception date attribute, a facility number attribute, a cable attribute, a pair attribute, a repair package attribute, a maintenance analyst name attribute, a trouble message attribute, a telephone number attribute, a tea attribute and a test result attribute. The number of exceptions per wire center occurring on a selected summary date is calculated in response to receiving a summary request from the user system. The summary request includes the selected summary date and input to the calculating is the selected summary date and the ALIT database. The number of exceptions per wire center occurring on the summary date is transmitted to the user system via the network in response to the calculating. User records located in the ALIT database that include a selected wire center and a selected detail date are transmitted to the user system via the network in response to receiving from the user system a wire center detail request. The wire center detail request includes the selected wire center and the selected detail date. The ALIT database is updated with repair package information in response to receiving an add repair package request via the network. The add repair package request includes a wire center, a facility, a cable, an exception date, a repair package number, a low pair and a high pair.
In a further aspect, a computer program product for analyzing automatic line insulation testing data comprises a storage medium readable by a processing circuit and storing instructions for execution by the processing circuit for performing a method comprising receiving an electronic version of ALIT test results and parsing the ALIT test results to extract error data. The error data is inserted into an ALIT database. The ALIT database includes one record for each exception located in the error data and each record includes: a wire center attribute, an exception date attribute, a facility number attribute, a cable attribute, a pair attribute, a repair package attribute, a maintenance analyst name attribute, a trouble message attribute, a telephone number attribute, a tea attribute and a test result attribute. The number of exceptions per wire center occurring on a selected summary date is calculated in response to receiving a summary request from a user. The summary request includes the selected summary date and input to the calculating is the selected summary date and the ALIT database. The number of exceptions per wire center occurring on the summary date is transmitted to the user in response to the calculating. User records located in the ALIT database that include a selected wire center and a selected detail date are transmitted to the user in response to receiving from the user a wire center detail request. The wire center detail request includes the selected wire center and the selected detail date. The ALIT database is updated with repair package information in response to receiving an add repair package request. The add repair package request includes a wire center, a facility, a cable, an exception date, a repair package number, a low pair and a high pair.
BRIEF DESCRIPTION OF THE DRAWINGS
Referring to the exemplary drawings wherein like elements are numbered alike in the several FIGURES:
FIG. 1 is a block diagram of an exemplary system for analyzing ALIT data;
FIG. 2 is flow diagram of an exemplary process for creating an ALIT database for analyzing ALIT data;
FIG. 3 is an exemplary ALIT database record;
FIG. 4 is a flow diagram of an exemplary process for utilizing an ALIT database for analyzing ALIT data;
FIG. 5 is an exemplary user interface for viewing a list of the number of exceptions per wire center for a particular day;
FIG. 6 is an exemplary user interface for viewing a list of all exceptions for the selected wire center;
FIG. 7 is an exemplary user interface for entering repair package information into the ALIT database;
FIG. 8 is a flow diagram of an exemplary process for analyzing the decision process of a MA when a repair package was created;
FIG. 9 is an exemplary user interface for viewing a list of the number of repair packages built per month by each MA;
FIG. 10 is an exemplary user interface for viewing a list of all repair packages built in a selected month by a particular MA; and
FIG. 11 is an exemplary user interface for viewing the test data utilized by a MA when the MA decided to build the repair package.
DETAILED DESCRIPTION OF THE INVENTION
A method for analyzing automatic line insulation testing (ALIT) data is presented. The method identifies exceptions that need to be handled without going through the paper report. When an MA gets to work in the morning the ALIT information has already been processed and stored in an ALIT database. In an exemplary embodiment of the present invention, the MA logs on to a computer system and selects a district to be analyzed. The MA then views a list of the exception counts by wire center on the computer screen. The report automatically excludes exceptions that have already been addressed by repair packages. The MA may then select a wire center to drill down to the details of the exceptions for the wire center. The exceptions for each cable are grouped together and are color coded to indicate that the exceptions pertain to the same cable. The MA may then analyze the data and build repair packages. An exemplary embodiment of the present invention allows the MA to analyze ALIT data without having to sift through large volumes of paper and without having to be knowledgeable in database search tools (e.g., SQL).
In FIG. 1 , a block diagram of an exemplary system for facilitating the analysis of ALIT data is generally shown. The exemplary system includes a host system 110 located in a central office operating as an application server. The host system 110 executes a tool called ALIT and dumps the results to a commercially available tool called Predictor, which compiles morning reports detailing ALIT exceptions. The Predictor tool runs on the predictor system 112 . ALIT is performed nightly by equipment that sequentially tests lines in the central office for battery crosses and grounds. The Predictor reports that include the results of all the tests, including good cables and cables with battery crosses and grounds are sent to a printer. In an exemplary embodiment of the present invention, the Predictor reports are printed to a virtual printer and the reports are stored in a storage device 108 connected (directly or via a network) to the host system 110 .
The system in FIG. 1 also includes one or more user systems 102 through which MAs located at one or more geographic locations may contact the host system 104 to initiate the execution of the ALIT analysis process. In an exemplary embodiment of the present invention, the host system 104 executes the ALIT analysis application program and the user system 102 is coupled to the host system 104 via a network 106 . Each user system 102 may be implemented using a general-purpose computer executing a computer program for carrying out the processes described herein. The user system 102 may be a personal computer (e.g., a lap top, a personal digital assistant) or a host attached terminal. If the user system 102 is a personal computer, the processing described herein may be shared by a user system 102 and the host system 104 (e.g., by providing an applet to the user system 102 ).
The network 106 may be any type of known network including, but not limited to, a wide area network (WAN), a local area network (LAN), a global network (e.g. Internet), a virtual private network (VPN), and an intranet. The network 106 may be implemented using a wireless network or any kind of physical network implementation known in the art. A user system 102 may be coupled to the host system through multiple networks (e.g., intranet and LAN) so that not all user systems 102 are coupled to the host system 104 through the same network. One or more of the user systems 102 and the host system 104 may be connected to the network 106 in a wireless fashion. In an exemplary embodiment, the user system 102 is connected to the host system 104 via an intranet and the host system 104 executes the ALIT analysis application software.
The storage device 108 may be implemented using a variety of devices for storing electronic information. It is understood that the storage device 108 may be implemented using memory contained in the host system 104 or it may be a separate physical device. The storage device 108 is logically addressable as a consolidated data source across a distributed environment that includes a network 106 . The physical data may be located in a variety of geographic locations depending on application and access requirements. Information stored in the storage device 108 may be retrieved and manipulated via the host system 104 . The storage device 108 includes an ALIT database. The storage device 108 may also include other kinds of data such as information concerning the creation of the ALIT database records (e.g., date and time of creation). In an exemplary embodiment of the present invention, the host system 104 operates as a database server and coordinates access to application data including data stored on storage device 108 .
The host system 104 depicted in FIG. 1 may be implemented using one or more servers operating in response to a computer program stored in a storage medium accessible by the server. The host system 104 may operate as a network server (e.g., a web server) to communicate with the user system 102 . The host system 104 handles sending and receiving information to and from the user system 102 and can perform associated tasks. The host system 104 may reside behind a firewall to prevent unauthorized access to the host system 104 and enforce any limitations on authorized access. A firewall may be implemented using conventional hardware and/or software as is known in the art.
The host system 104 may also operate as an application server. The host system 104 executes one or more computer programs to facilitate the analysis of ALIT data. One of the computer programs is the ALIT analysis application program. Processing may be shared by the user system 102 and the host system 104 by providing an application (e.g., java applet) to the user system 102 . Alternatively, the user system 102 may include a stand-alone software application for performing a portion or all of the processing described herein. As previously described, it is understood that separate servers may be utilized to implement the network server functions and the application server functions. Alternatively, the network server, the firewall, and the application server may be implemented by a single server executing computer programs to perform the requisite functions.
FIG. 2 is flow diagram of an exemplary process for creating an ALIT database for analyzing ALIT data. At step 202 , the ALIT is executed in the central office. At step 204 , the ALIT results are transmitted to the Predictor system 112 . The Predictor software compiles a morning report for each wire center at step 206 . Next, at step 208 , the Predictor software transmits the morning report to a virtual printer 208 , located on a storage device 108 . In this manner, the Predictor software does not need to be modified to utilize an exemplary embodiment of the present invention because the Predictor software sends output to the storage device 108 in the same manner that it already sends output to a printer. At step 210 , the software located on the host system 104 parses the text of the Predictor reports (e.g., extracts only exception records) and inserts the data into an ALIT database located on the storage device 108 . Finally, at step 220 , the MAs may access the data in the ALIT database via a network.
FIG. 3 is an exemplary ALIT database located on the storage device 108 and created by step 210 in FIG. 2 . The database includes an entry, or record, for each exception in the Predictor report. Each entry includes attributes such as: wire center 302 ; maintenance analyst name 304 ; exception date 306 ; repair package 308 (blank if no repair package has been built for the exception and filled in with a repair package number if the MA has built a repair package for the exception); facility number 310 ; cable 312 ; pair 314 within the cable; trouble message 316 ; telephone number 318 affected by the exception; terminal address (TEA) 320 ; and test result 322 . In an exemplary embodiment of the present invention, the ALIT database is a relational database to allow for easy sorting, manipulating and reporting of the ALIT data, however other database management systems may be implemented. Alternate embodiments of the present invention may include a subset of these attributes and/or additional attributes depending on installation requirements. In the exemplary embodiment of the ALIT database depicted in FIG. 3 , the attributes are sourced from the Predictor reports. In an alternate embodiment of the present invention, attributes from other sources may be combined with the Predictor report database based on installation requirements.
FIG. 4 is a flow diagram of an exemplary process that a MA may follow when utilizing an ALIT database for analyzing ALIT data. At step 402 the MA may view a list that includes the number of exceptions per wire center for a particular day. FIG. 5 is an exemplary user interface screen for viewing a list of the number of exceptions per wire center for a particular day. The user interface screen includes a table with one line for each wire center 302 . The columns of the table include: wire center 302 ; maintenance analyst name 304 ; maximum packages 502 (the field supervisor's estimate at how many packages his team can handle); total number of exceptions 504 in the wire center 302 ; and exception date 306 . With the exception of the maximum packages 502 column, the information in the user interface screen depicted in FIG. 5 is derived by executing a query against the data contained in the ALIT database.
Referring back to FIG. 4 , at step 404 , the MA may select a wire center 302 from the user interface screen depicted in FIG. 5 by “clicking on” a particular wire center 302 on the screen. At step 406 , a list of all the exceptions for the selected wire center is presented to the MA. FIG. 6 is an exemplary user interface for viewing a list of all exceptions for the selected wire center. The user interface screen includes a table with one line for each exception. The columns of the table include: repair package 308 ; facility number 310 ; cable 312 ; pair 314 ; trouble message 316 ; telephone number 318 ; TEA 320 and test result 322 . The user interface screen is also color coded and sorted by cable so that a MA may quickly identify which exceptions belong to the same cable. For example, the first line 602 is an exception for cable number thirteen and the second four lines 604 are exceptions for cable number eleven hundred and forty-four.
The table in FIG. 6 does not include exceptions that have already been addressed (e.g., by building a repair package) by the MA so that the MA can focus on those exceptions that may possibly need to be addressed. In an alternate exemplary embodiment, the table depicted in FIG. 6 only includes cables that have three or more exceptions, and/or the table is sorted with the cables having the highest number of exceptions coming first. Any number of sort orders and selection criteria may be utilized with an exemplary embodiment of the present invention to build the screen depicted in FIG. 6 . The sort order and selection criteria for the table may be modified (e.g., for the entire system, for a particular wire center, for a particular MA, for a particular day) as required. To build a repair package for one or more exceptions the MA selects, or “clicks on” the repair package 308 column in the table.
Referring back to FIG. 4 , a MA may decide to build a repair package that includes one or more exceptions at step 408 . The decision to build a repair package may be based on many factors such as the number of failures and/or the severity of failures for a particular cable. In an exemplary embodiment of the present invention, the MA enters a separate system to build a repair package and then returns to the ALIT analysis application program to enter information about the repair package. FIG. 7 is an exemplary user interface for entering repair package information into the ALIT database. The user interface displays the wire center 302 , the facility number 310 , the cable 312 and the exception date 306 . The user is prompted to enter the number associated with the repair package 308 , the low pair 314 included in the repair package 308 and the high pair 314 included in the repair package 308 . When the MA selects submit 702 the information is added into the ALIT database. In an alternate exemplary embodiment of the present invention, the system that builds the repair package is integrated with the ALIT analysis system to automatically update the ALIT database with the information when a repair package is built. This may be accomplished by having the ALIT analysis system extract information from the system that builds the repair packages or by having the repair package building system sending the information to the ALIT database.
FIG. 8 is a flow diagram of an exemplary process for analyzing the decision process of a maintenance analyst when a repair package was created. This may be useful in refining the decision process used by the MAs to determine when to create a repair package and to track the types of exceptions that actually require a repair package for correction. At step 802 , a MA supervisor or MA may select the report option. At step 804 , the MA supervisor is presented with a list of the number of repair packages built per month by each MA FIG. 9 is an exemplary user interface for viewing a list of the number of repair packages built per month by each MA. The user interface screen in FIG. 9 includes a table with one line for each MA. The MA is identified by a common user identification (CUID) 902 which corresponds to the MA name 304 . For each CUID 902 a year to date total 904 of all repair packages built as well as the total number of repair packages built on a monthly basis 906 are displayed. The values in these columns may be calculated using data contained in the ALIT database.
Referring back to FIG. 8 , at step 806 , the MA supervisor selects a month for a particular MA by “clicking on” the month in the user interface screen depicted in FIG. 9 . At step 808 , the MA supervisor may view a list of all repair packages built in the selected month for the selected MA. FIG. 10 is an exemplary user interface for viewing a list of all repair packages built in a selected month by a particular MA. The MA supervisor is presented with a table that includes one line for each repair package built during the selected month. The columns include wire center 302 , exception date 306 , facility number 310 , cable 312 , low pair 314 , high pair 314 and repair package 308 . Again, the data in these columns is derived from the contents of the ALIT database.
At step 810 in FIG. 8 , the MA supervisor may select a particular repair package to understand the criteria utilized by the MA in creating the repair package by “clicking on” the repair package field in FIG. 10 . At step 812 , the ALIT test results the MA utilized when deciding to build the repair package are displayed. FIG. 11 is an exemplary user interface for viewing the test data utilized by a MA when the MA decided to build the repair package. The user interface screen includes a table with one line for each exception. The columns of the table include: facility number 310 ; cable 312 ; pair 314 ; trouble message 316 ; telephone number 318 ; TEA 320 and test result 322 . The user interface screen is also color coded and sorted by cable so that a MA supervisor may quickly identify which exceptions belong to the same cable. For example, the first three lines 1102 are exceptions for cable number one and the next three lines 1104 are exceptions for cable number thirteen.
These reports may be utilized by a MA supervisor for evaluation and training of MAs and they could point out the need for modified criteria for building repair packages. These reports are examples of the type of information that may be gleaned from the ALIT database. Other sort orders and content are possible in an alternate exemplary embodiment of the present invention. In addition, the reports may be entered into a spreadsheet package (e.g., Excel) and/or e-mailed to a field technician if there is some question about whether a repair package should have been created. An alternate embodiment of the present invention includes creating a report that shows the status of ALIT in all offices. The report may filter out only those offices that require attention because ALIT has not executed. In this manner a MA may know whether the data in the ALIT database is complete.
An embodiment of the present invention organizes ALIT exception data in an on-line database. This may lead to increased analysis speed because a MA is no longer required to sift through a massive report to identify and group exceptions to build a repair package. In contrast, an embodiment of the present invention groups together exceptions based on exception date and cable so that the MA may easily identify and analyze exceptions. In addition, using an automated on-line database may lead to a decrease in the number of errors in terms of repair packages that weren't built that should have been built and repair packages that were built that didn't need to be built. This may lead to an increased reliance by technicians in the field on the repair packages being built and delivered. Further, the ability to analyze the data that a MA had available on a particular date may lead to improving the repair package building analysis process. An embodiment of the present invention may also lead to a cost savings in terms of the amount of paper that may be saved. Finally, a value may be attached to fixing exceptions more quickly in terms of both MA time savings and customer good will.
As described above, the embodiments of the invention may be embodied in the form of computer-implemented processes and apparatuses for practicing those processes. Embodiments of the invention may also be embodied in the form of computer program code containing instructions embodied in tangible media, such as floppy diskettes, CD-ROMs, hard drives, or any other computer-readable storage medium, wherein, when the computer program code is loaded into and executed by a computer, the computer becomes an apparatus for practicing the invention. An embodiment of the present invention can also be embodied in the form of computer program code, for example, whether stored in a storage medium, loaded into and/or executed by a computer, or transmitted over some transmission medium, such as over electrical wiring or cabling, through fiber optics, or via electromagnetic radiation, wherein, when the computer program code is loaded into and executed by a computer, the computer becomes an apparatus for practicing the invention. When implemented on a general-purpose microprocessor, the computer program code segments configure the microprocessor to create specific logic circuits.
While the invention has been described with reference to exemplary 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 appended claims. 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. | A method for analyzing automatic line insulation testing data comprising receiving an electronic version of ALIT test results and parsing the ALIT test results to extract error data. The error data is inserted into an ALIT database. The ALIT database includes one record for each exception located in the error data and each record includes: a wire center attribute, an exception date attribute, a facility number attribute, a cable attribute, a pair attribute, a repair package attribute, a maintenance analyst name attribute, a trouble message attribute, a telephone number attribute, a tea attribute and a test result attribute. The number of exceptions per wire center occurring on a selected summary date is calculated in response to receiving a summary request from a user. The summary request includes the selected summary date and input to the calculating is the selected summary date and the ALIT database. The number of exceptions per wire center occurring on the summary date is transmitted to the user in response to the calculating. User records located in the ALIT database that include a selected wire center and a selected detail date are transmitted to the user in response to receiving from the user a wire center detail request. The wire center detail request includes the selected wire center and the selected detail date. The ALIT database is updated with repair package information in response to receiving an add repair package request. The add repair package request includes a wire center, a facility, a cable, an exception date, a repair package number, a low pair and a high pair. | 7 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] Not Applicable
STATEMET OF FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] Not Applicable
BACKGROUND OF THE INVENTION
[0003] 1. TECHNICAL FIELD
[0004] This invention relates in general to integrated circuits and, more particularly, to a method and apparatus for electronic design automation.
[0005] 2. Description of the Related Art
[0006] In the design of integrated circuits, a “place and route” tool is often used aid in the physical layout of a circuit. After the logic for a circuit is designed and tested, the cells of the circuit must be arranged in such a manner that desired timing (and other) constraints are met. A place and route tool can iterate through different layouts and evaluate timing constraints for each layout until a suitable solution is reached.
[0007] As integrated circuits become denser, the layout of the circuit with respect to timing constraints becomes more critical and difficult. In a design that combines a large number of gates and aggressive timing criteria, it can be extremely difficult for a place and route tool to complete its task. In cases with many timing constraints, the place and route tool may not be able to complete all routes, as some constraints may be impossible to meet, or the number of iterations needed may be unacceptable.
[0008] Therefore, a need has arisen for a place and route system that allows flexible placement of critical paths to meet aggressive timing performances.
BRIEF SUMMARY OF THE INVENTION
[0009] In the present invention, an integrated circuit design includes datapath cells in a structured layout and other cells in an unstructured layout. A description of a desired layout for the datapath cells is generated and transferred to a place and route tool, in order to assign the desired layout to the datapath cells within the place and route tool. The datapath cells are assigned a predetermined status to prevent movement of the cells. Constraint information regarding the other cells is then transferred to the place and route tool and optimization procedures may be performed on the layout based on desired criteria, such that the datapaths cells are unmoved as different layout iterations are performed on the other cells.
[0010] The present invention provides several advantages over the prior art. The approach described above allows the layout designer to address both timing performance and density. Structured cells may be place in matrices that are not “hard macros”; therefore, they can be any shape that makes sense from a timing point of view. The placer can take advantage of the free space within matrices for improving density. Overall timing-driven placement is improved, since the place and route tool always has a global view of all timing constraints and can optimize the layout of no-fixed cell placements.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0011] For a more complete understanding of the present invention, and the advantages thereof, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which:
[0012] [0012]FIG. 1 illustrates a block diagram of a system incorporating a place and route tool with enhanced control over the layout of structured elements;
[0013] [0013]FIG. 2 illustrates a flow chart describing the operation of the system of FIG. 1;
[0014] [0014]FIG. 3 a illustrates a matrix used to define the layout of cells in the place and route tool;
[0015] [0015]FIG. 3 b illustrates spacing between matrix rows;
[0016] [0016]FIG. 3 c illustrates the use of spacing between rows to achieve interleaved matrices; and
[0017] [0017]FIG. 4 illustrates space left in structured layout matrices used for unstructured cells.
DETAILED DESCRIPTION OF THE INVENTION
[0018] The present invention is best understood in relation to FIGS. 1 - 4 of the drawings, like numerals being used for like elements of the various drawings.
[0019] [0019]FIG. 1 illustrates a block diagram showing the overall structure of a system 10 for placing and routing cell in a complex circuit that provides full control on the placement of highly critical structured logic. A place and route tool 12 , receives information from a datapath generator 14 that defines the desired layout for the structured logic (also referred to herein as the “datapath” cells) in a language configuration file compatible with the place and route tool. Information for the remainder of the cells (also referred to herein as the “control” or “unstructured” cells) is input from input source 16 , which could be a file or input device. The datapath generator 14 and place and route tool 12 may be implemented on the same or separate workstations or similar computing devices.
[0020] [0020]FIG. 2 is a flowchart describing the basic operation of the system 10 of FIG. 1. In block 18 , the cell information for the circuit is entered into the place and route tool 12 . In block 20 , the datapath generator 12 , which is a program that generates a file describing the desired layout information for the datapath cells, generates a configuration file. This configuration file defines the layout of the datapath cells of the circuit. The datapath generator 14 allows the layout designer to have complete control of the placement of these cells. This aspect is described in greater detail hereinbelow.
[0021] In block 22 , the datapath logic layout is “fixed” in the place and route tool 12 . In the AVANT! APOLLO product, cells may be fixed through assignment of a “fixed” status to the cells, which provides the highest layout priority; the placement location of these cells is guaranteed as other cells are moved to optimize timing performance.
[0022] In step 24 , timing (or other) constraints for the remaining unstructured cells (the “control logic”) are submitted to the place and route tool 12 . The place and route tool 12 can optimize the layout in step 26 , without affecting the previously-fixed placement of the datapath logic. When timing (or other) constraints are met, the layout information can be generated in block 28 .
[0023] The present invention as described in FIGS. 1 and 2 provides the layout designer with the ability to carefully and flexibly place critical structured logic in a desired arrangement, which will not be affected by subsequent optimization routines by the place and route tool 12 .
[0024] [0024]FIGS. 3 a - c illustrate the placement of the structured logic in greater detail. The illustrated embodiment uses the operation of the AVANT! APOLLO place and route tool as an example of how the structured datapath logic can be allocated in a place and route tool; other products may use different methods of allocating cells in a matrix.
[0025] [0025]FIG. 3 a illustrates an empty matrix 30 . A cell matrix is defined, at a minimum, by a unique name, a number of rows 34 and a number of columns 36 . Each slot 32 of an empty matrix is initially square, i.e., the height and width of each slot 32 is the height of the unit tile cell. Each slot 32 is assigned a row and column number. Once a cell is assigned to a slot 32 , the corresponding matrix column 36 is enlarged according to the cell width of the slot 32 .
[0026] Column and row space can be adjusted by adding extra space between rows 34 or between columns 36 . In FIG. 3 b , extra space 38 is added between rows 34 . This feature can be used to allow two or more matrices to be interleaved, as shown in FIG. 3 c by matrices 30 a and 30 b , having rows 34 a and 34 b , respectively. Accordingly, datapaths made of cells of different widths can be efficiently placed. Using this method, complex datapaths can be built using basic standard cells, without the need for custom cell development. It should be noted that two or more matrices may be interleaved using interleaved columns, as well as interleaved rows as shown in FIG. 3 c.
[0027] When timing-driven tools have difficulties with complex constraints, the datapath matrix (or matrices) can ensure timings for the critical paths. By adjusting column and row spacing, free space 38 can be planned within the matrix to allow timing-driven placement of embedded standard cells along with the structured placement cells. FIG. 4 illustrates free space 38 within one or more matrices for further placement of timing-driven unstructured cells. It has been found that this approach provides improved density by increasing the percentage of area utilization (by gates) compared to an approach where datapath blocks are placed as embedded hard macros.
[0028] Implementation of the method of FIG. 2 requires three parts: logic synthesis, datapath description file, and placement automation. These aspects are described below.
[0029] To have more control over the way the logic synthesis is done to achieve the expected netlist, datapaths are descried as dedicated modules. Also, each datapath basic element is described as a “box”, either containing a basic RTL (register transfer level) description for the involved function, or direct instantiation of the involved cell.
[0030] All datapath modules are instantiated within the RTL description of the integrated circuit, leading to a structural type of description. Once the RTL description is ready, logic synthesis is performed using a bottom-up approach: datapath basic elements are synthesized first and the top level is synthesized using the “fixed” attribute on basic element instances. For accurate timing analysis, the net loads corresponding to structural placements are annotated either from the previous layout run or from estimated load values.
[0031] Once the DSP core netlist is ready, the involved instances can be identified and collected through wildcards and a description file for the corresponding matrix can be easily built. The syntax of the description file is very simple and the requested information about the involved matrices are: matrix name, number of rows, number of columns, space between rows, space between columns, matrix location, strap pitch and involved instances per row. Strap pitch allows planning for vertical power ground straps by adding convenient space at locations within the matrices.
[0032] Location can be absolute or relative to the location of another matrix. Relative location is useful for cases of further floorplan updates. If the floorplan is changed and if the location of all matrices depends on the location of the reference matrix, then the only requested manual change will be to move the latter matrix. Also, this feature allows the designer to try various datapath implementations, since the cost of manual intervention is very low.
[0033] Rows are concisely described using patterns and indices. Three examples are:
[0034] ROWx=“pattern” index_start=index_end=index step=pattern_width=
[0035] ROWx=“pattern1 pattern2” index_start=index_end=index step=pattern_width=
[0036] ROWx=“pattern1” index_start=index_end=index step=pattern_width=, “pattern2” index_start=index_end=index step=pattern width=, “pattern3” index_start=index_end=index step=pattern_width=
[0037] From this description file, the Datapath generator produces a full scheme language configuration file for involved matrices, allowing installation of structured placement within the floorplan.
[0038] An example of a description file is:
[0039] ROW0=‘acc0_reg_@INDEX@/data_reg_reg” INDEX_start=0 INDEX_end=38 INDEX_step=2 PATTERN_WIDTH=66.3
[0040] ROW1=‘acc1_reg_@INDEX@/data_reg_reg” INDEX_start=0 INDEX_end=38 INDEX_step=2 PATTERN_WIDTH=66.3
[0041] ROW2=‘acc2_reg_@INDEX@/data_reg_reg” INDEX_start=0 INDEX_end=38 INDEX_step=2 PATTERN_WIDTH=66.3
[0042] ROW3=‘acc3_reg_@INDEX@/data_reg_reg” INDEX_start=0 INDEX_end=38 INDEX_step=2 PATTERN_WIDTH=66.3
[0043] ROW4=‘acc0_reg_@INDEX@/data_reg_reg” INDEX_start=39 INDEX_end=1 INDEX_step=−2 PATTERN_WIDTH=66.3
[0044] ROW1=‘acc1_reg_@INDEX@/data_reg_reg” INDEX_start=39 INDEX_end=1 INDEX_step=−2 PATTERN_WIDTH=66.3
[0045] ROW2=‘acc2_reg_@INDEX@/data_reg_reg” INDEX_start=39 INDEX_end=1 INDEX_step=−2 PATTERN_WIDTH=66.3
[0046] ROW3=‘acc3_reg_@INDEX@/data_reg_reg” INDEX_start=39 INDEX_end=1 INDEX_step=−2 PATTERN_WIDTH=66.3
[0047] The eight-line description set forth above provides placement for 152 cells within the regular structure.
[0048] Once all description files are generated for the datapaths, the datapath generator 14 passes the language configuration file to the place and route tool 12 to install all datapath logic within the floorplan, taking into account power/ground pre-routing. If relative placements are used, rework in order to try various placement scenarios or in case of floorplan change will be minimal.
[0049] When all floorplan matrices are installed within the floorplan, all involved cells are pre-placed with the fixed status, which is the highest priority. After all structure placements are installed, the usual place and route procedures are executed. The constraints for the rest of the standard unstructured cells are input into the place and route tools, and are placed using automated procedures, such as timing-driven placement. These procedures may make use of the porosity of the datapath matrices to place the rest of the standard cells.
[0050] If favorable to placement criteria, such as timing specification, and if free space is available among structured placement, standard cells can be placed within datapaths. Then routing can be performed to complete the layout.
[0051] The present invention provides several advantages over the prior art. The approach described above allows the layout designer to address both timing performance and density. Matrices are not “hard macros”; therefore, they can be any shape that makes sense from a timing point of view. The placer can take advantage of the free space within matrices for improving density. Overall timing-driven placement is improved, since the place and route tool always has a global view of all timing constraints and can optimize the layout of no-fixed cell placements.
[0052] Although the Detailed Description of the invention has been directed to certain exemplary embodiments, various modifications of these embodiments, as well as alternative embodiments, will be suggested to those skilled in the art. The invention encompasses any modifications or alternative embodiments that fall within the scope of the claims. | A layout system ( 10 ) includes a place and route tool ( 12 ) and a datapath layout generator. The datapath layout generator ( 14 ) provides a mechanism for the designer to place datapath cells in a structured arrangement. The datapath layout generator ( 14 ) sends a language configuration file to the place and route tool ( 12 ) to install the datapath structure. The datapath structure assigned “fixed” status, which prevents the place and route tool ( 12 ) from moving the datapath cells in later operations. Constraints for the remaining cells are then installed in the place and route tool ( 12 ), and criteria-driven placement, such as timing-driven placement, can be used to arrange these cells in an optimum fashion. The remaining cells can be placed in open areas of the datapath structure for improved density. | 6 |
BACKGROUND OF THE INVENTION
[0001] Diatomite (diatomaceous earth) is a marine sedimentary rock. This substance can be found in lake deposits consists mainly of accumulated shells or hydrous silica secreted by diatoms which are microscopic organisms, chemically consists of silicon dioxide (SiO 2 ) which is essentially inert; is ionically attacked by strong alkali and hydrofluoric acids. Other components of diatomite are: sand, clay, volcanic ash, magnesium carbonate, soluble salts and organic matter.
[0002] The types and amounts of impurities are highly variable and depend on the sedimentation conditions and the time of diatomite disposition. Diatomites are used primarily:
[0003] 1) as filters
[0004] 2) as insulating material
[0005] 3) as filler material
[0006] In the first case the substances are used for waste sludge filters, due to its high porosity and heat resistance (melting point close to 1593° C.), this material is used as thermal insulator and for this its structure may be in the form of aggregate powder or bricks. Its use as a filler material is due to the fact that after this material is used, its reuse is not recommended, because it is contaminated by absorbed substances or products, hence its application for filling.
[0007] The uses of diatomaceous earth are very widely applicable, as the case of sugar refining, as well as in the production of solvents, antibiotics, fats and oils; these materials are also very importantly used in paint and paper industries.
[0008] This research bears some similarity to Patent CN 19969696118706, Dec. 31, 1997/Jun. 14, 1996 to Hong bin Liu, but in this case a rough concrete was developed for specific purposes, in our work, we are proposing a furnace to produce materials, such as bricks, lattices and ceramic materials for construction; also, in patent JP08319143A2, 3 Dec. 1996, Denki Kagaru proposed a method for obtaining a product which is mixed with cement, in our case, we propose a furnace, wherein the flue gases are absorbed and the obtained material has the adequate grain size to be mixed with binding agents for use in the building industry, diatomaceous earth has also been recycled to produce ceramic material according to patent JP00086397A2, Mar. 28, 2000. The difference with our work is that we start from waste to obtain a useful and highly competitive material.
[0009] There is other work on the incineration of waste JP54128477, Oct. 5, 1979 to which calcium sulfate is added and is solidified with an accelerator, our work involves obtaining material, grinding and screening the same prior to treatment with binding agents, so it also differs from this latest research.
OBJECT OF THE INVENTION
[0010] The present invention has as an object using granular solid industrial waste materials that are harmful to the environment and which are from diatomaceous earth, which, when mixed with binding agents, water or other granular solid waste as: tailings, foundry sand and volcanic ash in said mixture, new building or ceramic materials can be produces which are compression-resistant, have low porosity, resistant to abrasion and fatigue tests and weighing 25% less than conventional materials like bricks, lattices, tiles, pipes, drywall. The new materials are useful in the construction industry, and also the obtained ceramic materials can be applied in the field of mechanical engineering.
DETAILED DESCRIPTION OF THE INVENTION
[0011] This process is characterized by having a furnace which removes organic material that adheres to the diatomaceous earth to achieve homogenization in the incineration process, and has pedestal agitator, which is a device whose function is to lower a set of blades and removing the material treated into the furnace. It also has a viewing window to see the process that takes place in the furnace, the gases generated during the process are removed by an exhaust, and conducted to the absorber where they are neutralized. The details of the process used in the furnace to treat filter earth waste as a construction material are shown in the following description and the accompanying figures.
[0012] FIG. 1 presents an overview of the manner in which the process of treatment of diatomaceous earth is carried out until the obtainment of the material to be used in the construction industry. With reference to said figure and the description of the devices, the diatomaceous earth contaminated dynamic material absorbed during the process, is deposited in the container ( 1 ) which is the container for storing the industrial waste, and which is located on a folding table ( 2 ) and a hoist ( 15 ) which serves to introduce and remove material from the furnace; the sample is subsequently placed in the furnace ( 3 ) which is the system to perform the heat treatment to the residue; when is already placed in this point the sample has a pedestal agitator ( 4 ) which is a device used to lower the blades and remove material treated in the furnace for approximately 60 minutes and keeping the temperature of 850° C. During this time the sample is stirred every 10 minutes. To watch the ignition process it has a window ( 17 ). The gases generated from the combustion or burning of waste are cooled by a system ( 5 ) consisting of a jacket with water inlet and outlet, the gases are conducted through a pump ( 6 ) directly to the absorber ( 7 ) by this device it is prevented that the gases are emitted into the atmosphere. This system is coupled to a valve ( 16 ) for extracting samples. Once treated, the industrial waste the container ( 1 ) is extracted and empties its contents into the hopper ( 8 ); from this vessel, the sample is passed to the mill ( 9 ) where the sample obtains a grain size ranging between 100 and 200 μm, subsequently passed to a sieve ( 10 ) where the sample is sieved, about 500 g of this mixture is collected and mixed using the cracking method and then a sample of 50 g is taken from this same material to carry out the qualitative and quantitative chemical analysis, using analytical techniques such as Plasma Emission Spectrometry or Atomic Absorption, in order to determine the presence and concentration of heavy metals in the chemical matrix of the granular solid industrial waste. In case of observing in the chemical analyses metal concentrations less than or equal to the limits allowed by law, in this situation the sample is deposited directly on the conveyor belt ( 11 ).
[0013] In case of observing the presence and concentration of metals at levels higher than allowed by the regulations in metals such as chromium, lead, or vanadium, we proceed to perform the extraction or leaching using reducing agents, complexing agents and surfactants, the time used for the operation is 120 minutes, the temperature of 60° C. and the pH ranges were 2, 5, 7, and 10. This step is performed in order to test the pH, allowing to optimally solubilize metals within the leaching solution. The process and apparatus used for leaching are done following the methodology described in U.S. Pat. No. 5,356,601 from 1994, U.S. Pat. No. 5,376,000 from 1994; Mexican Patent No. 1,867,902 from 1997. Concluding the leaching process, the sample is filtered, dried in a furnace at 80° C.; after that the sample is deposited in a conveyor belt ( 11 ) whose function is to guide the sample to a mixer ( 13 ) where other granular solids residues (such as tailings or foundry sand or volcanic ash) are added previously treated in thermostated columns, wherein the samples are leached using reducing agents, complexing agents and surfactants. The time used for the operation is 120 minutes, a temperature of 60° C. and the pH ranges are 2, 5, 7 and 10, following the leaching methodology described U.S. Pat. No. 5,356,601 from 1994, U.S. Pat. No. 5,376,000 from 1994; Mexican Patent No. 1,867,902 from 1997. After leaching, the samples are filtered, dried in a furnace at 80° C. and 33% by volume of granular solid waste, 33% by volume of diatomaceous earth, 34% by volume of binding agents are added, sufficient supplementary water is added until obtaining a mixture ( 13 ). After combining the ingredients for 15 minutes, the mixture is poured into molds ( 14 ).
Methodology for Performing the Post and Molding
[0014] Both bricks and blocks for walls and ceilings can be manufactured with mortars based on regular and lightweight aggregates. Among the main objectives to be achieved with these building elements are: to lighten buildings, increased insulation and ease of operation. Light inert materials are generally chosen, diatomaceous earth very well satisfy the above objectives because we obtained materials whose compressive strength was 235 kg/cm 2 and their water absorption percentage was of 21%. Both tests were conducted under international standards. On other hand, the manufacture may be accomplished by conveniently dosed mortars and concretes, with fluid, pasty or dry consistency depending on the ensuing system and the piece to be molded.
[0015] In case that the qualitative and quantitative chemical analysis indicate the presence of heavy metals in the samples of granular, solid industrial residues, such as Pb, Cr, Ni, Cu, etc. at concentrations greater than those permitted by law in diatomaceous earth chemical matrices, the leaching process needs to be done using the thermostated columns, similarly as was done with mining granular, solid industrial waste (tailings) or with granular solid waste from the automotive industry (foundry sand).
[0016] a) Preparation of the Post.
[0017] In our research, for making bricks, tubes, tiles, drywall, lattices, a paste composed of diatomaceous earth base obtained from industrial waste is used (which was submitted to the standard CRETIB, resulting negative, thus ensuring that the product obtained it is not harmful or toxic to be used) as well as tailings, foundry sand, volcanic ash and binding agents. The mixture of the above components is kneaded with a suitable amount of water without exceeding its plasticity. For making bricks an average of 33% by volume of diatomaceous earth, 13% by volume of tailings, 10% by volume of volcanic ash, 10% by volume of foundry sand and 34% by volume of binder agent were used, yielding bricks with an average weight less than 1 kg with the following dimensions: length 25 cm, width 12 cm, and 8 cm thick.
[0018] b) mold If the molding is done by direct compression or by vibrating, the mortar or concrete must be dry. If the process is made by casting, they must be fluid. The processes may be manual or mechanical depending on the production, cost and product quality. In our case we used the manual procedure because the individually manufactured pieces were for laboratory analysis and not for commercial use. We used metal and wooden molds; the procedure was as follows.
EXAMPLES
[0019] 1) Brick Manufacturing
[0020] Bricks measuring 25 cm long, 12 cm wide and 8 cm thick were manufactured with an average weight of 974 g. Use was made of 33% by volume of diatomaceous earth, 13% by weight of tailings, 10% by volume of volcanic ash, 10% by volume of foundry sand and 34% by volume of binder agent (cement is used as binder). As a result of mechanical tests applied to cubes of 2 inches per side, according to the ASTM standard 170-50, an average compressive strength of 272.3 kg/cm 2 was obtained, also the water percent absorption was 17% which meant that the obtained material absorbs less water than specified in ASTM standard 121-48, which has 21% maximum water absorption percentage.
[0021] 2) Lattice Manufacturing Lattices were produced whose geometric shape was square with curved vertices and a centered circle with 8 cm diameter, the height was of 40 cm and each side is 25 cm and the thickness is 12 cm. For manufacturing the lattices, we used on average 33% by volume of diatomaceous earth, 13% by weight of tailings, 10% by volume of foundry sand, 10% of volcanic ash and 34% by volume of binding agent (cement was used as binders) with each piece having an average weight of 3000 g. The physical and mechanical properties of the lattices were similar to those of the obtained bricks.
[0022] 3) Ceramics Manufacturing
[0023] Ceramic materials (bricks, lattices and various specimens) were manufactured whose dimensions were similar to those outlined in Examples 1 and 2, combined with 20-33% by volume of granular solid waste from diatomaceous earths and other 20-33% of granular solid residues (tailings, foundry sand, volcanic ash), these residues had the particularity that the heavy metals present in their chemical matrix were leached prior to their application for manufacturing ceramic materials. To perform the leaching thermostated coupled columns were used, as binding agents 10-20% by volume clay or kaolin were used, as well as 10-14% by volume of feldspar and sufficient water was used to make a paste which was poured into molds, preheating to 100° C. When the water contained in the samples was evaporated, these were transferred to another furnace at a temperature between 1000-1200° C. The obtained materials had an average compression strength of 264 kg/cm 2 , which means these products have a compressive strength about 3 times higher than conventional materials. Also, they practically have any porosity and their weight was between 25-30% lower than brick or lattices made with conventional materials. | The invention relates to a method and furnace allowing the use of filter earth (diatomaceous earth) waste, in which the organic material is removed using the method of the application. The furnace comprises a container in which the industrial waste is deposited, and a folding table is used to transport the material. The invention also includes an agitator with a base, used to lower blades and remove the treated material. The gases generated are collected by an extractor which includes a cooling jacket and are subsequently sent to an absorber system in which they are neutralised. Said device and method are used to obtain lightweight materials with low porosity and high compression strength, rendering solid granular industrial waste that is dangerous to the environment suitable for use in the construction or mechanical industries. | 2 |
BACKGROUND AND SUMMARY
In certain vehicle accidents, it may be difficult, impossible, or unsafe to exit from the doors of the vehicle. In a vehicle roll-over, for example, one door is under the cab and the other door facing upward. In heavy trucks especially, the weight of the door makes it difficult to lift open and hold open, both for an emergency responder and more so for a vehicle occupant attempting this from the inside of the vehicle cab. Egress through the windshield frame may be the fastest and safest alternative.
The windshields in heavy trucks may be designed so that the windshield can be kicked out in the event exit from the doors is difficult or unsafe. If the driver or passenger is not able to kick out the windshield, however, response team personnel must attempt to remove the windshield with tools, usually by cutting it out. This is laborious and time-consuming, and may pose a safety concern, for example, if there is a fire in or around the vehicle, or if the occupants of the vehicle are in need of immediate medical attention.
Methods for dislodging or removing windshields, windows, and doors are known. For example, U.S. Pat. No. 3,737,193 to Cain discloses a collapsed tube disposed about a periphery of a windshield and connected to a high pressure fluid source that inflates the tube when an impact sensor senses the vehicle has been in a collision. Expansion of the tube dislodges the windshield from its mounting. U.S. Pat. No. 3,741,583 to Usui et al. discloses a pyrotechnic device that releases or destroys a windshield or window in a vehicle using the vehicle airbag triggering system to activate it.
While the art discloses systems that activate upon sensing a collision or impact on the vehicle, none are known that respond to a vehicle roll-over, which involves different dynamics than front end or side collisions. For example, an event leading to a roll-over may begin with a front end collision, which in prior system may trigger the windshield release system before event concludes, that is, before the vehicle comes to a rest. The dislodged windshield, now movable, may then pose a danger to the vehicle occupants. As another example, a roll-over may result from a driver attempting a curve at too high a rate of speed, which may involve no frontal collision and a side impact that may not be sufficient to trigger the system.
The invention provides a system for dislodging a vehicle windshield from its mounting automatically upon a vehicle roll-over event.
According to an embodiment of the invention, a system for detaching a windshield from a vehicle cab, comprises a pressure applying device mounted between a windshield and a frame element, a roll-over condition sensor, and a controller connected to receive a signal indicating a roll-over condition from the roller-over condition sensor and connected to activate the pressure applying device responsive to receiving said signal.
The invention, according to another aspect, may further comprise an acceleration condition sensor, the controller being connected to receive a signal indicating an acceleration condition from the acceleration condition sensor, and further configured to activate the pressure applying device responsive to receiving the roll-over condition signal and the acceleration condition signal. According to a preferred embodiment, the acceleration sensor generates a signal when vehicle acceleration ends, that is, when the vehicle has come to a rest. The acceleration sensor may alternatively or in addition be configured to detect a collision event, as in vehicle airbag systems.
In addition or alternatively, the controller is configured with a delay function to delay activating the pressure applying device for a predetermined time period following receipt of a signal indicating a roll-over condition from the roller-over condition sensor.
According to an alternative embodiment, a system of the invention includes the controller being connected to a vehicle device controlling deployment of a vehicle airbag system to receive a signal indicating deployment of the airbag. The controller is configured to use both the roll-over condition sensor and the airbag deployment sensor to trigger the pressure applying device.
According to the invention, a pressure applying device comprises at least one pyrotechnic device. A mounting device for a pyrotechnic device includes a frame element that contains and directs the energy from activated the pyrotechnic device toward the windshield to weaken or break the securing elements.
Alternatively, a pressure applying device comprises an inflatable tube and a gas generating device connected to inflate the tube upon receipt of a signal from the controller.
Other pressure applying devices may be employed, as the invention is not directed to a particular pressure applying device.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood by reference to the following detailed description read in conjunction with the appended drawings, in which:
FIG. 1 is a schematic of a windshield dislodging system according to an embodiment of the invention;
FIG. 2 is a schematic of a windshield dislodging system according to an alternative embodiment;
FIG. 3 is simplified section view of an embodiment for mounting a pyrotechnic device to a windshield mounting structure according to a first type; and,
FIG. 4 is a simplified section view of an embodiment for mounting a pyrotechnic device to a windshield mounting structure according to a second type.
DETAILED DESCRIPTION
FIG. 1 illustrates schematically an automatic windshield dislodging system in accordance with an embodiment of the invention. The system includes a controller 20 that is operatively connected to at least one pressure applying device 21 disposed in a vehicle windshield mounting frame 10 . The at least one pressure applying device 21 is configured to dislodge a windshield 12 from the mounting frame 10 upon a signal from the controller 20 . By dislodge is meant releasing the windshield 10 from the mounting structure so that it is displaced from the frame or is otherwise readily movable by a person outside the vehicle.
As illustrated, a plurality of pressure applying devices 21 are provided and are distributed on the periphery of the windshield frame 10 so to apply pressure at several points around the frame. In this embodiment, each of the plurality of pressure applying devices 21 is connected to the controller 20 for activation. The pressure applying device may be a pyrotechnic device, such as is used for inflating airbags in vehicles, which generates in a short time highly pressurized gas, which will be directed against the windshield. Those skilled in the art will know how to select a pyrotechnic device having an appropriate energy release to dislodge the windshield.
Alternatively, as shown in FIG. 2 , the pressure applying device may be embodied as an inflatable tube 30 disposed about the periphery of the mounting frame in a position so that upon inflation, the tube applies pressure to the windshield 12 . A source of pressurized gas 23 , for example, a pyrotechnic device, is connected to the tube and activatable by the controller 20 . A pyrotechnic device is convenient as the source for rapid inflation of the tube, as is known in the airbag art. A single pyrotechnic device may be used, which will be selected to generate sufficient gas to inflate the tube to an appropriate pressure. Alternatively, two or more smaller pyrotechnic devices may be connected to various points on the tube, for example, to ensure simultaneous expansion of the tube about the periphery of the windshield 12 .
Returning to FIG. 1 , the controller 20 is connected to receive a signal from a vehicle roll-over sensor or detector 40 . The roll-over sensor 40 detects a condition when the vehicle is no longer in a wheels-down attitude and generates a signal for the controller 20 . The controller 20 receives the roll-over condition signal and generates a signal to activate the pressure applying device or devices 21 .
According to a preferred embodiment, upon receipt of the roll-over signal, the controller 20 initiates a timer (not illustrated) to delay activation of the pressure generating device. The time delay may be chosen, for example, to be of sufficient duration so that the vehicle will likely have come to rest before the windshield is dislodged from the frame.
The time delay may also be used to avoid activating the system based on a spurious roll-over signal. After the time delay expires, the controller 20 will check that the roll-over signal is still valid before activating the pressure applying device.
According to yet another alternative, the system may include an acceleration sensor 50 connected to the controller 20 to deliver a signal relating to the acceleration condition of the vehicle. The acceleration sensor 50 may be configured to detect a collision, which results in a rapid acceleration or deceleration. The controller 20 will use this signal as a check on the validity of the vehicle condition requiring windshield dislodgement, the presence of both a collision condition and roll-over condition indicating an event where release of the windshield is needed.
Alternatively, the acceleration sensor 50 may be configured to detect when the vehicle has come to a rest, that is, the deceleration of the vehicle to a stop. This signal may be used by the controller 20 in place of the time delay, or in conjunction with the time delay, to determine when to activate the pressure generating device.
FIG. 3 shows a side section view, in highly simplified form, of an example of a windshield mounting frame 60 adapted for the invention. The frame 60 in FIG. 3 is of the type in which an elastomeric extrusion 61 retains the windshield 12 and seals the frame 60 . The extrusion 61 has an S-shape profile with oppositely facing channels. One channel 63 receives a frame edge 65 , while the other channel 67 receives the windshield 12 . The frame 60 is modified to support the pressure applying device, which may be the pyrotechnic device 21 or the inflatable tube 30 . A member 69 having an arcuate profile is provided to support the device 21 , 30 and direct the energy of the expansion of gas toward the windshield 12 and extrusion 61 . The member 69 may be a continuous channel formed on the inner periphery of the frame 60 , as illustrated. Alternatively, in the case of the pyrotechnic device 21 , the member may be configured as individual retaining members, such as cup shaped members, fastened to the frame 60 at appropriate locations.
FIG. 4 shows another example of windshield mounting frame 80 adapted for the invention. The frame 80 is configured to bond the windshield 12 with a layer of bonding material 81 applied between the frame and an outer periphery of the windshield. The frame 80 includes a member 83 having a cup-shaped profile to support the pressure applying device 21 , 30 and direct the energy of the gas expansion to the windshield 12 , as in the embodiment of FIG. 3 . The member 83 may be formed as a channel at an inner periphery of the frame 80 . Alternatively, in the case of the pyrotechnic device 21 , the member 83 may be configured as individual retaining members, such as cup shaped members, fastened to the frame 80 at appropriate locations.
The invention has been described in terms of preferred principles, embodiments, and components; however, those skilled in the art will recognize that equivalents may be substituted for what is described without departing from the scope of the invention as defined in the appended claims. | A system for automatically detaching a windshield from a vehicle cab comprises a pressure applying device mounted between a windshield and a frame element, a roll-over condition sensor, and a controller connected to receive a signal indicating a roll-over condition from the roller-over condition sensor and connected to activate the pressure applying device responsive to receiving said signal. The pressure applying device may be one or more pyrotechnic devices. The system includes a delay function to delay activating the pressure applying device to allow the vehicle to come to a rest. | 1 |
FIELD OF THE DISCLOSURE
[0001] The present disclosure is generally directed toward communications and more specifically toward contact centers.
BACKGROUND
[0002] The work assignment logic in contact centers usually makes only a single routing decision for a contact at a single point in time. It is conventional wisdom that making a single routing decision on a work item results in the most efficient use of resources. The work assignment decision is, therefore, based on a single state of the contact center. This limits the work assignment logic from making perfect contact-to-agent assignments if the perfect agent is not currently available at the time when the assignment decision is made.
SUMMARY
[0003] It is with respect to the above issues and other problems that the embodiments presented herein were contemplated. In particular, embodiments of the present disclosure provide the ability to defer work assignment decisions in a contact center based on one or both of the following considerations: value-based deferment and skill-based deferment.
[0004] In a value-based deferment scheme the following process may be employed: (1) a service time goal (target time) is set for contacts in the contact center; (2) a first percentage of the target time is defined and expected losses are associated with that first percentage of the target time; (3) agents are split into at least two tiers (more tiers are possible) where a tier 1 agent is expected to earn a first amount for handling contacts of a certain type and a tier 2 agent is expected to earn a second amount (which is less than the first amount) for handling contacts of the same type; (4) the tiers may be based on agent skill, but do not necessarily have to be based on agent skill—rather, it can be based on actual Key Performance Indicators (KPIs) for the agents; and (5) a deferment rule is defined such that during periods of agent surplus (e.g., when tier 2 agents are available, but the tier 1 agents are not available) the work assignment decision is deferred for an amount of time equal to the actual wait time of the contact plus the first percentage unless a tier 1 agent becomes available. Prior to this amount of time elapsing, tier 2 agents are not considered eligible to receive the contact, even though the tier 2 agents are actually qualified to handle the contact. Accordingly, the work assignment decision is actually being processed but no agent-to-contact assignment decision is made because the tier 2 agents are not considered eligible. After the requisite amount of time has passed, the tier 2 agents become eligible and the best suited tier 2 agent among the available tier 2 agents is assigned to the contact (unless a tier 1 agent has become available in the meantime). This deferment scheme can be expanded to support more than two tiers of agents. In particular, up to N (where N is greater than or equal to 2) tiers of agents can be established along with up to N−1 incremental deferment stages. The example of two tiers and a single deferment decision will be described for ease of understanding the principles of the present disclosure.
[0005] In a skill-based deferment scheme the following process may be employed: (1) a service time goal (target time) is set for contacts in the contact center; (2) agents are split into at least two tiers (more tiers are possible) where a tier 1 agent is expected to process contacts of a certain type in a first amount of time and a tier 2 agent is expected to process contacts of the same type in a second amount of time (which is greater than the first amount of time by a delta time that is calculated based on expected losses for using a tier 2 agent as compared to a tier 1 agent to handle the contact); (3) the tiers may be based on agent skill, but do not necessarily have to be based on agent skill—rather, it can be based on actual KPIs for the agents; and (5) a deferment rule is defined such that during periods of agent surplus (e.g., when tier 2 agents are available, but the tier 1 agents are not available) the work assignment decision is deferred for an amount of time equal to the delta time unless a tier 1 agent becomes available. Prior to this amount of time elapsing, tier 2 agents are not considered eligible to receive the contact. Accordingly, the work assignment decision is actually being processed but no agent-to-contact assignment decision is made because the tier 2 agents are not considered eligible. After the delta time has passed, the tier 2 agents become eligible and the best suited tier 2 agent among the available tier 2 agents is assigned to the contact (unless a tier 1 agent has become available in the meantime).
[0006] The tiered approach described herein is much easier to implement than previously-available solutions. Specifically, the administrator only has to define a first percentage of target time (e.g., 1%, 5%, 7%, etc.) and that percentage can be applied across every skill or work type. Additionally, multiple tiers can be easily defined because the system administrator only has to define multiple percentages and define the routing rules that occur after a percentage-based threshold has been crossed. These rules can be defined across multiple skills for any type of agent rather than applying specific threshold rules for different types of agents at different skills.
[0007] In accordance with at least some embodiments of the present disclosure, a method is provided which generally comprises:
dividing a group of contact center agents into at least two tiers, the at least two tiers including a first tier and a second tier; receiving a work item at a first time, wherein agents from the group of contact center agents are qualified to process the received work item; determining that no first tier agent is available to receive the work item; and deferring a work assignment decision for the work item regardless of whether or not a second tier agent is available to receive the work item, wherein the work assignment decision is deferred until a second time that is a predetermined amount of time after the first time.
[0012] The phrases “at least one”, “one or more”, and “and/or” are open-ended expressions that are both conjunctive and disjunctive in operation. For example, each of the expressions “at least one of A, B and C”, “at least one of A, B, or C”, “one or more of A, B, and C”, “one or more of A, B, or C” and “A, B, and/or C” means A alone, B alone, C alone, A and B together, A and C together, B and C together, or A, B and C together.
[0013] The term “a” or “an” entity refers to one or more of that entity. As such, the terms “a” (or “an”), “one or more” and “at least one” can be used interchangeably herein. It is also to be noted that the terms “comprising”, “including”, and “having” can be used interchangeably.
[0014] The term “automatic” and variations thereof, as used herein, refers to any process or operation done without material human input when the process or operation is performed. However, a process or operation can be automatic, even though performance of the process or operation uses material or immaterial human input, if the input is received before performance of the process or operation. Human input is deemed to be material if such input influences how the process or operation will be performed. Human input that consents to the performance of the process or operation is not deemed to be “material”.
[0015] The term “computer-readable medium” as used herein refers to any tangible storage that participates in providing instructions to a processor for execution. Such a medium may take many forms, including but not limited to, non-volatile media, volatile media, and transmission media. Non-volatile media includes, for example, NVRAM, or magnetic or optical disks. Volatile media includes dynamic memory, such as main memory. Common forms of computer-readable media include, for example, a floppy disk, a flexible disk, hard disk, magnetic tape, or any other magnetic medium, magneto-optical medium, a CD-ROM, any other optical medium, punch cards, paper tape, any other physical medium with patterns of holes, a RAM, a PROM, and EPROM, a FLASH-EPROM, a solid state medium like a memory card, any other memory chip or cartridge, or any other medium from which a computer can read. When the computer-readable media is configured as a database, it is to be understood that the database may be any type of database, such as relational, hierarchical, object-oriented, and/or the like. Accordingly, the disclosure is considered to include a tangible storage medium and prior art-recognized equivalents and successor media, in which the software implementations of the present disclosure are stored.
[0016] The terms “determine”, “calculate”, and “compute,” and variations thereof, as used herein, are used interchangeably and include any type of methodology, process, mathematical operation or technique.
[0017] The term “module” as used herein refers to any known or later developed hardware, software, firmware, artificial intelligence, fuzzy logic, or combination of hardware and software that is capable of performing the functionality associated with that element. Also, while the disclosure is described in terms of exemplary embodiments, it should be appreciated that individual aspects of the disclosure can be separately claimed.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] The present disclosure is described in conjunction with the appended figures:
[0019] FIG. 1 is a block diagram of a communication system in accordance with embodiments of the present disclosure;
[0020] FIG. 2 is a block diagram depicting pools and bitmaps that are utilized in accordance with embodiments of the present disclosure;
[0021] FIG. 3 is a block diagram depicting a data structure in accordance with embodiments of the present disclosure; and
[0022] FIG. 4 is a flow diagram depicting a method of deferring work item routing decisions in accordance with embodiments of the present disclosure.
DETAILED DESCRIPTION
[0023] The ensuing description provides embodiments only, and is not intended to limit the scope, applicability, or configuration of the claims. Rather, the ensuing description will provide those skilled in the art with an enabling description for implementing the embodiments. It being understood that various changes may be made in the function and arrangement of elements without departing from the spirit and scope of the appended claims.
[0024] FIG. 1 shows an illustrative embodiment of a communication system 100 in accordance with at least some embodiments of the present disclosure. The communication system 100 may be a distributed system and, in some embodiments, comprises a communication network 104 connecting one or more communication devices 108 to a work assignment mechanism 116 , which may be owned and operated by an enterprise administering a contact center in which a plurality of resources 112 are distributed to handle work items (in the form of contacts) from the customer communication devices 108 .
[0025] In accordance with at least some embodiments of the present disclosure, the communication network 104 may comprise any type of known communication medium or collection of communication media and may use any type of protocols to transport messages between endpoints. The communication network 104 may include wired and/or wireless communication technologies. The Internet is an example of the communication network 104 that constitutes an Internet Protocol (IP) network consisting of many computers, computing networks, and other communication devices located all over the world, which are connected through many telephone systems and other means. Other examples of the communication network 104 include, without limitation, a standard Plain Old Telephone System (POTS), an Integrated Services Digital Network (ISDN), the Public Switched Telephone Network (PSTN), a Local Area Network (LAN), a Wide Area Network (WAN), a Session Initiation Protocol (SIP) network, a cellular network, and any other type of packet-switched or circuit-switched network known in the art. In addition, it can be appreciated that the communication network 104 need not be limited to any one network type, and instead may be comprised of a number of different networks and/or network types. As one example, embodiments of the present disclosure may be utilized to increase the efficiency of a grid-based contact center. Examples of a grid-based contact center are more fully described in U.S. patent application Ser. No. 12/469,523 to Steiner, the entire contents of which are hereby incorporated herein by reference. Moreover, the communication network 104 may comprise a number of different communication media such as coaxial cable, copper cable/wire, fiber-optic cable, antennas for transmitting/receiving wireless messages, and combinations thereof
[0026] The communication devices 108 may correspond to customer communication devices. In accordance with at least some embodiments of the present disclosure, a customer may utilize their communication device 108 to initiate a work item, which is generally a request for a processing resource 112 . Exemplary work items include, but are not limited to, a contact directed toward and received at a contact center, a web page request directed toward and received at a server farm (e.g., collection of servers), a media request, an application request (e.g., a request for application resources location on a remote application server, such as a SIP application server), and the like. The work item may be in the form of a message or collection of messages transmitted over the communication network 104 . For example, the work item may be transmitted as a telephone call, a packet or collection of packets (e.g., IP packets transmitted over an IP network), an email message, an Instant Message, an SMS message, a fax, and combinations thereof.
[0027] In some embodiments, the communication may not necessarily be directed at the work assignment mechanism 116 , but rather may be on some other server in the communication network 104 where it is harvested by the work assignment mechanism 116 , which generates a work item for the harvested communication. An example of such a harvested communication includes a social media communication that is harvested by the work assignment mechanism 116 from a social media network or server. Exemplary architectures for harvesting social media communications and generating work items based thereon are described in U.S. patent application Ser. Nos. 12/784,369, 12/706,942, and 12/707,277, filed Mar. 20, 1010, Feb. 17, 2010, and Feb. 17, 2010, respectively, each of which are hereby incorporated herein by reference in their entirety.
[0028] The format of the work item may depend upon the capabilities of the communication device 108 and the format of the communication. In some embodiments, work items are logical representations within a contact center of work to be performed in connection with servicing a communication received at the contact center (and more specifically the work assignment mechanism 116 ). The communication associated with a work item may be received and maintained at the work assignment mechanism 116 , a switch or server connected to the work assignment mechanism 116 , or the like until a resource 112 is assigned to the work item representing that communication at which point the work assignment mechanism 116 passes the work item to a routing engine 132 to connect the communication device 108 which initiated the communication with the assigned resource 112 . The connection between the customer communication device 108 and a resource 112 may be effected by the routing engine 132 assigning one or more communication resources (e.g., sockets, buffers, physical ports, etc.) to establish a communication path (e.g., media stream such as RTP or SRTP) between the communication device 108 and resource 112 . In some embodiments, the communication path established between the communication device 108 and resource 112 may also carry call control signaling, however, it may also be possible to maintain the signaling path at the work assignment mechanism 116 .
[0029] Although the routing engine 132 is depicted as being separate from the work assignment mechanism 116 , the routing engine 132 may be incorporated into the work assignment mechanism 116 or its functionality may be executed by the work assignment engine 120 .
[0030] In accordance with at least some embodiments of the present disclosure, the communication devices 108 may comprise any type of known communication equipment or collection of communication equipment. Examples of a suitable communication device 108 include, but are not limited to, a personal computer, laptop, Personal Digital Assistant (PDA), cellular phone, smart phone, telephone, or combinations thereof. In general each communication device 108 may be adapted to support video, audio, text, and/or data communications with other communication devices 108 as well as the processing resources 112 . The type of medium used by the communication device 108 to communicate with other communication devices 108 or processing resources 112 may depend upon the communication applications available on the communication device 108 .
[0031] In accordance with at least some embodiments of the present disclosure, the work item is sent toward a collection of processing resources 112 via the combined efforts of the work assignment mechanism 116 and routing engine 132 . The resources 112 can either be completely automated resources (e.g., Interactive Voice Response (IVR) units, processors, servers, or the like), human resources utilizing communication devices (e.g., human agents utilizing a computer, telephone, laptop, etc.), or any other resource known to be used in contact centers.
[0032] As discussed above, the work assignment mechanism 116 and resources 112 may be owned and operated by a common entity in a contact center format. In some embodiments, the work assignment mechanism 116 may be administered by multiple enterprises, each of which has their own dedicated resources 112 connected to the work assignment mechanism 116 .
[0033] In some embodiments, the work assignment mechanism 116 comprises a work assignment engine 120 which enables the work assignment mechanism 116 to make intelligent routing decisions for work items. In some embodiments, the work assignment engine 120 is configured to administer and make work assignment decisions in a queueless contact center, as is described in U.S. patent application Ser. No. 12/882,950, the entire contents of which are hereby incorporated herein by reference.
[0034] More specifically, the work assignment engine 120 can generate bitmaps/tables 128 and determine, based on an analysis of the bitmaps/tables 128 , which of the plurality of processing resources 112 is eligible and/or qualified to receive a work item and further determine which of the plurality of processing resources 112 is best suited to handle the processing needs of the work item. As will be discussed in further detail herein, the work assignment engine 120 may comprise one or more rule sets for making intelligent work item routing decisions, which in some embodiments may actually be a decision to defer a work item routing decision for a predetermined amount of time.
[0035] In situations of work item surplus, the work assignment engine 120 can also make the opposite determination (i.e., determine optimal assignment of a work item to a resource). In some embodiments, the work assignment engine 120 is configured to achieve true one-to-one matching by utilizing the bitmaps/tables 128 and any other similar type of data structure.
[0036] The work assignment engine 120 may reside in the work assignment mechanism 116 or in a number of different servers or processing devices. In some embodiments, cloud-based computing architectures can be employed whereby one or more components of the work assignment mechanism 116 are made available in a cloud or network such that they can be shared resources among a plurality of different users.
[0037] In addition to comprising the work assignment engine 120 , the work assignment mechanism 116 may also comprise a state monitor 124 . The state monitor 124 may be configured to monitor and assess the state of the contact center 100 on a continual or periodic basis and provide results of its assessment to the work assignment engine 120 . Specifically, the state monitor 124 may provide its analysis information to the work assignment engine 120 to assist the work assignment engine 120 in making work item routing decisions. In some embodiments, the input from the state monitor 124 may be used as inputs to the decision rules contained in the work assignment engine 120 . More specifically, the work assignment engine 120 may comprise one or more value-based deferment rules 136 and/or one or more skill-based deferment rules 140 . The variable or considerations of these deferment rules 136 , 140 may include data received from the state monitor 124 .
[0038] Specifically, the state monitor 124 may be responsible for monitoring one or more agent performance metrics (e.g., KPIs, schedule adherence, overall profitability, skill improvements, etc.) for some or all agents in the contact center 100 and comparing those metrics with one or more Service Level Objectives or SLOs. The results of these comparisons may be provided to work assignment engine 120 to assist in making work item routing decisions.
[0039] Information monitored by the state monitor 124 may include information which describes an agent's current or historical (e.g., past hour, day, week, month, quarter, year, recent work assignment history, etc.) performance within the contact center. In some embodiments, the state monitor 124 may provide KPI information that is obtained from the work assignment engine 120 or from some other analysis and reporting module running within the contact center. As used herein, KPIs may include, without limitation, any metric or combination of metrics that define performance of an entity within a contact center (e.g., a contact center agent, a group of contact center agents, etc.). Specifically, a KPI can be defined in terms of making progress toward strategic goals or simply the repeated achievement of some level of an operational goal.
[0040] In a contact center context, KPIs may vary depending upon whether work items correspond to outbound contacts (e.g., contacts originated by the contact center) or inbound contacts (e.g., contacts received at the contact center that have been originated outside the contact center). Non-limiting examples of outbound contact KPIs include: Contacts per hour—Average number of customers a call center agent was able to contact within an hour; Leads Conversion Rate—The percentage of leads that actually converted to sales; Hourly Sales—The average amount of sales the call center representative was able to close in an hour; Daily Sales—The average value of sales the agent was able to close in a day; and Accuracy—Extent to which a contact has been handled according to a predetermined script.
[0041] Non-limiting examples of inbound contact KPIs include: Real time Q—Metrics; Calls per hour—The average number of calls the agent is able to take per hour; Saves/One-Call Resolutions—The number of times our agents are able to resolve an issue immediately within the first phone call. Colloquially referred to as “one-and-done” calls; Average Handle Time—How long it takes for one call to be handled, which includes the call time itself, plus the work done after that call; Average Wait Time—How long a caller is put on hold before a call center agent becomes available to take the call; Accuracy; Abandonment Rate—This is the percentage of customers who disconnected before an agent was able to intercept the call; and Completion Rate—The ratio of successfully finished calls to the number of attempted calls by the customer.
[0042] Other types of KPIs that are not necessarily specific to inbound or outbound contacts include, without limitation, customer satisfaction level, customer service level, average speed of answer, contact forecast precision level, quality of services rendered, average handling cost of a contact, agent occupancy ratio, schedule adherence and conformity, and time distribution (in service, non-service detailed time or “shrinkage”). Other examples include number of times calls are put on hold, number of transfers, $/min, $/call, number of upsells, number of cross-sells, etc.
[0043] As can be appreciated, the state monitor 124 and/or bitmaps/tables 128 may be internal to the work assignment mechanism 116 or they may be separate from the work assignment mechanism 116 . Likewise, certain components of the work assignment engine 120 (e.g., value-based deferment rules 136 and skill-based deferment rules 140 ) do not necessarily need to be executed within the work assignment engine 120 and may be executed in different parts of the contact center 100 .
[0044] FIG. 2 depicts exemplary data structures 200 which may be incorporated in or used to generate the bitmaps/tables 128 used by the work assignment engine 120 . The exemplary data structures 200 include one or more pools of related items. In some embodiments, three pools of items are provided, including an enterprise work pool 204 , an enterprise resource pool 212 , and an enterprise qualifier set pool 220 . The pools are generally an unordered collection of like items existing within the contact center. Thus, the enterprise work pool 204 comprises a data entry or data instance for each work item within the contact center 100 at any given time.
[0045] In some embodiments, the population of the work pool 204 may be limited to work items waiting for service by or assignment to a resource 112 , but such a limitation does not necessarily need to be imposed. Rather, the work pool 204 may contain data instances for all work items in the contact center regardless of whether such work items are currently assigned and being serviced by a resource 112 or not. The differentiation between whether a work item is being serviced (i.e., is assigned to a resource 112 ) may simply be accounted for by altering a bit value in that work item's data instance. Alteration of such a bit value may result in the work item being disqualified for further assignment to another resource 112 unless and until that particular bit value is changed back to a value representing the fact that the work item is not assigned to a resource 112 , thereby making that resource 112 eligible to receive another work item.
[0046] Similar to the work pool 204 , the resource pool 212 comprises a data entry or data instance for each resource 112 within the contact center. Thus, resources 112 may be accounted for in the resource pool 212 even if the resource 112 is ineligible due to its unavailability because it is assigned to a work item or because a human agent is not logged-in. The ineligibility of a resource 112 may be reflected in one or more bit values. As discussed in further detail herein, the eligibility of a resource 112 may differ from the availability of that resource 112 to handle work as determined by the deferment rules 136 , 140 . Specifically, depending upon an agent's assigned tier according to one or more deferment rules 136 , 140 , an agent may actually be available to handle work items, but may be ineligible to handle work items of a particular type (e.g., skill requirement). The available but ineligible status of an agent may allow the deferment rules 136 , 140 to actually defer work item routing decisions for a period of time, perhaps in the hope that a better qualified agent will become available and eligible in the meantime.
[0047] The qualifier set pool 220 comprises a data entry or data instance for each qualifier set within the contact center. In some embodiments, the qualifier sets within the contact center are determined based upon the attributes or attribute combinations of the work items in the work pool 204 . Qualifier sets generally represent a specific combination of attributes for a work item. In particular, qualifier sets can represent the processing criteria for a work item and the specific combination of those criteria. Each qualifier set may have a corresponding qualifier set identified “qualifier set ID” which is used for mapping purposes. As an example, one work item may have attributes of language=French and intent=Service and this combination of attributes may be assigned a qualifier set ID of “12” whereas an attribute combination of language=English and intent=Sales has a qualifier set ID of “13.” The qualifier set IDs and the corresponding attribute combinations for all qualifier sets in the contact center may be stored as data structures or data instances in the qualifier set pool 220 .
[0048] In some embodiments, one, some, or all of the pools may have a corresponding bitmap. Thus, a contact center may have at any instance of time a work bitmap 208 , a resource bitmap 216 , and a qualifier set bitmap 224 . In particular, these bitmaps may correspond to qualification bitmaps which have one bit for each entry. Thus, each work item in the work pool 204 would have a corresponding bit in the work bitmap 208 , each resource 112 in the resource pool 212 would have a corresponding bit in the resource bitmap 216 , and each qualifier set in the qualifier set pool 220 may have a corresponding bit in the qualifier set bitmap 224 .
[0049] In some embodiments, the bitmaps are utilized to speed up complex scans of the pools and help each the work assignment engine make an optimal work item/resource assignment decision based on the current state of each pool. Accordingly, the values in the bitmaps 208 , 216 , 224 may be recalculated each time the state of a pool changes (e.g., when a work item surplus is detected, when a resource surplus is detected, etc.).
[0050] With reference now to FIG. 3 , a data structure 300 that may be used by one or both sets of deferment rules 136 , 140 will be described in accordance with embodiments of the present disclosure. The data structure 300 may comprise a number of data fields that enable the deferment rules 136 , 140 to intelligently defer work item routing decisions based on the current state of the contact center 100 . In some embodiments, the fields in the data structure 300 include a plurality of agent tier definition fields 304 a -N, a value-based deferment rule field 308 , a skill-based deferment rule 312 , and a service goal(s) field 316 .
[0051] As can be appreciated, the agent tier definition fields 304 a -N along with the deferment rule fields 308 , 312 may actually be integrated into the deferment rules 136 , 140 as appropriate. The data structure 300 may also be separated or duplicated among each different deferment rules 136 , 140 as appropriate. In other words, the value-based deferment rule 136 may comprise a first data structure that includes a first set of agent tier definition fields 304 a -N, a value-based deferment rule field 308 , and a service goal field 316 . The skill-based deferment rule 140 may comprise a second data structure that includes a second set of agent tier definition fields 304 a -N (different from the first set of agent tier definition fields), a skill-based deferment rule field 312 , and a service goal field 316 .
[0052] In some embodiments, the agent tier definition fields 304 a -N may comprise rules for assigning agents to agent tiers and/or an association between each agent in the contact center and their assigned tier. For instance, the first agent tier definition field 304 a may comprise a rule or definition for assigning a value of tier 1 to an agent. Alternatively, or in addition, the first agent tier definition field 304 a may comprise a listing of agents in the contact center 100 that have been assigned a value of tier 1.
[0053] It should be appreciated that agents may be assigned multiple different tier values for each skill in contact center. More specifically, an agent may be assigned a value of tier 1 for work items of a first type (e.g., a first skill), but a value of tier 2 or tier 3 for work items of a second type (e.g., a second skill). Accordingly, there may be different tier assignment definitions for each skill within the contact center. This means that deferment rules may vary according to the skill requirements of a work item. A first work item having a first set of skill requirements (or single skill requirement) may have a first deferment rule applied thereto whereas a second work item having a second set of skill requirements (or single skill requirement) may have a second deferment rule applied thereto.
[0054] Further still, depending upon the state of the contact center, the work assignment engine 120 may elect to either apply a value-based deferment rule 136 or a skill-based deferment rule 140 . As the state of the contact center changes, the work assignment engine 120 may switch between applying the different deferment rules 136 , 140 . In some embodiments, the decision to apply one deferment rule versus another deferment rule may depend upon whether and to what extent one or more service goals (also referred to as SLOs) as defined in the service goal field 316 are currently being met. As discussed above, a SLO is an objective for one or more pre-defined performance metrics that are currently being analyzed in the contact center 100 (perhaps by the state monitor 124 ).
[0055] If a particular SLO or set of SLOs are not being met, the work assignment engine 120 may decide to apply either the value-based deferment rule 136 or the skill-based deferment rule 140 . If multiple SLOs are not being met and some dictate that one deferment rule should be applied and others dictate that the other deferment rule should be applied, the work assignment engine 120 may be provided with logic that selects which deferment rule 136 , 140 should be applied in such a situation. The logic applied by the work assignment engine 120 in such a situation may be as simple as comparing the number of skill-related-SLOs being violated with the number of value-related-SLOs being violated and then selecting the appropriate deferment rule based on that comparison (e.g., if more skill-related-SLOs are being violated, then apply the skill-based deferment rule or if more value-related-SLOs are being violated, then apply the value-based deferment rule). Additional considerations may also be included in the selection analysis such as the relative importance to the contact center 100 of the SLOs being violated and to what extent the various SLOs are being violated.
[0056] With reference now to FIG. 4 , additional details related to the application of the deferment rules 136 , 140 will be described in accordance with embodiments of the present disclosure. The method depicted and described herein will refer to a two-tiered structure. However, it should be appreciated that embodiments of the present disclosure are not so limited and the concepts described in connection with FIG. 4 may be applied to situations where more than two agent tiers are defined and/or situations where multiple different agent tiers are defined for different skills in the contact center 100 . Furthermore, an agent may be assigned different tiers even for the same skill if the agent is highly efficient at handling work items for that skill, but is not particularly as good at extracting full value for the same work items. In this situation, the agent may be assigned a value of tier 1 if the skill-based deferment rules 140 are used to defer a routing decision, but the same agent may be assigned a value of tier 2 (or lower) if the value-based deferment rules 136 are used to defer a routing decision. Accordingly, an agent may be assigned a different tier for the same work item depending upon the state of the contact center 100 .
[0057] The method begins with the creation of agent tier definitions and the assignment of such definitions to the agents in the contact center 100 (step 404 ). Specifically, each agent may be assigned a tier value for one or both of the value-based deferment rules 136 and skill-based deferment rules 140 . Alternatively, the proficiency of an agent (e.g., skill-based proficiency and value-based proficiency) for every agent in the contact center may already be known and stored in a local database. The definition of tier definitions may simply involve defining a tier assignment rule that is applied to every agent in the contact center 100 .
[0058] The method continues when a work item is received at the contact center 100 and the associated attributes of the work item (e.g., skill or processing requirements) (step 408 ). This particular step may occur when the work item is received at the work assignment engine 120 . The attributes of the work item may be obtained using any known mechanisms such as obtaining information from a customer database, analyzing caller identification information, receiving information from an IVR interaction with the customer, etc.
[0059] After the attributes of the work item have been determined, the work assignment engine 120 continues by analyzing the resource pool 212 or the bitmap 216 associated therewith to determine whether any tier 1 agents are available (step 412 ). It should be appreciated that rather than referring to the bitmap 216 , if a queue-based contact center is being employed, the work assignment engine 120 may assign the work item to the appropriate queue and determine if any tier 1 agents are currently available in the associated resource queue. As noted above, the analysis of whether a tier 1 agent is available may depend upon whether the work assignment engine 120 is currently applying a value-based deferment rule 136 or a skill-based deferment rule 140 . The application of the value-based deferment rule 136 versus the skill-based deferment rule 140 may depend upon the current state of the contact center 100 as determined by information received from the state monitor 124 .
[0060] If a tier 1 agent is available to handle the received work item, then the method continues with the work assignment engine 120 selecting the best agent from the available tier 1 agents and assigning the work item to the best agent (step 436 ). In some embodiments, the best agent determination may be made by analyzing one or more of the bitmaps 208 , 216 , 224 . In a queue-based contact center, the selection of the best agent may be simplified in that the work assignment engine 120 may select the tier 1 agent that has been idle for the longest amount of time (e.g., the tier 1 agent has the highest queue position).
[0061] The work assignment engine 120 may provide the assignment information to the routing engine 132 to effect the work assignment decision (step 440 ). In particular, the routing engine 132 may establish a communication channel or communication session between the communication device 108 associated with the work item and the communication device of the selected tier 1 agent (e.g., the selected resource 112 ). The manner in which the communication channel or session is established may vary depending upon the nature of the work item/contact (e.g., whether the contact is a real-time or non-real-time contact).
[0062] Referring back to step 412 , if no tier 1 agents are currently available for the work item, then the method continues with the work assignment engine 120 analyzing the appropriate deferment rule 136 or 140 to determine if the work item routing decision should be deferred for a predetermined amount of time or not (steps 420 , 424 ). As discussed above, the deferment rule 136 , 140 analyzed by the work assignment engine 120 may depend upon whether and to what extent certain SLOs are being met. Other considerations that control which deferment rule should be used include whether the contact center is in a state of emergency, whether the state monitor 124 is predicting that one or more SLOs will not be met in the future, and any other condition of the contact center that might result in or is currently resulting in a decrease in the contact center's performance.
[0063] If the analysis of the appropriate deferment rule dictates that the work assignment decision should be deferred for a predetermined amount of time, then the method proceeds to step 428 where the work assignment engine 120 will cause the assignment decision to be deferred for that particular work item. During the deferment period, the hope is that a tier 1 agent will become available and the amount of time that was lost due to deferment will be offset by assigning the work item to a tier 1 agent instead of assigning the work item to a tier 2 (or lower) agent. The amount of time that an assignment decision is deferred may depend upon the deferment rule definitions and the number of SLOs that are currently being violated. It should be appreciated that if a relatively small number of SLOs (or less important SLOs) are being violated, then the deferment period can be longer than if a larger number of SLOs (or more important SLOs) are being violated. The importance of SLOs may be defined by a contact center manager or administrator and can be based on business rules or other considerations.
[0064] After the predetermined amount of time has passed (e.g., the assignment decision has been deferred for a first deferment period), the method returns to step 412 . If at step 424 it is determined that the work assignment decision should not be deferred (e.g., because the decision has already been deferred for the work item more than a predetermined number of times), the method proceeds with the work assignment engine 120 altering the eligibility of tier 2 agents (or lower tiers) to include more agents as eligible in the work assignment decision (step 432 ). The method is then depicted as proceeding to step 436 where a work assignment decision is made. However, it should be appreciated that if more than two tiers of agents are defined for the work item, then a second deferment period may be enforced after which additional tiers of agents may be switched from ineligible to eligible for handling the work item.
[0065] The work assignment decision made in step 436 after a deferment period has been enforced may be slightly different than if no deferment period has been enforced. Specifically, if during the deferment period a higher tier agent became available, then the work item can be assigned to the highest tiered or best agent. If no higher tier agent became available during the deferment period, then the work item can be assigned to the best suited available and eligible agent as dictated either by idle agent time (e.g., assign the work item to the agent that has been waiting the longest) or by analyzing the bitmaps 208 , 216 , 224 . It should be appreciated that the selection of a “best” agent will depend upon whether the contact center 100 is queue-based or queueless.
[0066] Accordingly, it should be appreciated that while embodiments of the present disclosure have been described in connection with a queueless contact center architecture, embodiments of the present disclosure are not so limited. In particular, those skilled in the contact center arts will appreciate that some or all of the concepts described herein may be utilized in a queue-based contact center or any other traditional contact center architecture.
[0067] Furthermore, in the foregoing description, for the purposes of illustration, methods were described in a particular order. It should be appreciated that in alternate embodiments, the methods may be performed in a different order than that described. It should also be appreciated that the methods described above may be performed by hardware components or may be embodied in sequences of machine-executable instructions, which may be used to cause a machine, such as a general-purpose or special-purpose processor (GPU or CPU) or logic circuits programmed with the instructions to perform the methods (FPGA). These machine-executable instructions may be stored on one or more machine readable mediums, such as CD-ROMs or other type of optical disks, floppy diskettes, ROMs, RAMs, EPROMs, EEPROMs, magnetic or optical cards, flash memory, or other types of machine-readable mediums suitable for storing electronic instructions. Alternatively, the methods may be performed by a combination of hardware and software.
[0068] Specific details were given in the description to provide a thorough understanding of the embodiments. However, it will be understood by one of ordinary skill in the art that the embodiments may be practiced without these specific details. For example, circuits may be shown in block diagrams in order not to obscure the embodiments in unnecessary detail. In other instances, well-known circuits, processes, algorithms, structures, and techniques may be shown without unnecessary detail in order to avoid obscuring the embodiments.
[0069] Also, it is noted that the embodiments were described as a process which is depicted as a flowchart, a flow diagram, a data flow diagram, a structure diagram, or a block diagram. Although a flowchart may describe the operations as a sequential process, many of the operations can be performed in parallel or concurrently. In addition, the order of the operations may be re-arranged. A process is terminated when its operations are completed, but could have additional steps not included in the figure. A process may correspond to a method, a function, a procedure, a subroutine, a subprogram, etc. When a process corresponds to a function, its termination corresponds to a return of the function to the calling function or the main function.
[0070] Furthermore, embodiments may be implemented by hardware, software, firmware, middleware, microcode, hardware description languages, or any combination thereof. When implemented in software, firmware, middleware or microcode, the program code or code segments to perform the necessary tasks may be stored in a machine readable medium such as storage medium. A processor(s) may perform the necessary tasks. A code segment may represent a procedure, a function, a subprogram, a program, a routine, a subroutine, a module, a software package, a class, or any combination of instructions, data structures, or program statements. A code segment may be coupled to another code segment or a hardware circuit by passing and/or receiving information, data, arguments, parameters, or memory contents. Information, arguments, parameters, data, etc. may be passed, forwarded, or transmitted via any suitable means including memory sharing, message passing, token passing, network transmission, etc.
[0071] While illustrative embodiments of the disclosure have been described in detail herein, it is to be understood that the inventive concepts may be otherwise variously embodied and employed, and that the appended claims are intended to be construed to include such variations, except as limited by the prior art. | A contact center is described along with various methods and mechanisms for administering the same. The contact center proposed herein provides the ability to, among other things, support deferring work item routing decisions for a predetermined amount of time even when agents that are technically qualified to handle the work item are available. The deferment of work item routing decisions helps to achieve better matching and, therefore, increases contact center efficiency even though decisions are delayed. | 7 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This is a Divisional Application of U.S. Ser. No. 10/632,430 filed Jul. 31, 2003 which application is hereby incorporated by reference in its entirety.
FIELD OF THE INVENTION
[0002] The present invention relates generally to polymer networks, methods of fabricating polymer networks and devices including polymer networks, and more particularly, to polymer networks formed from mixtures of reactive mesogens, methods of fabricating polymer networks formed from mixtures of reactive mesogens and devices including polymer networks formed from mixtures of reactive mesogens.
BACKGROUND OF THE INVENTION
[0003] The performance of electronic and display devices is continually being increased to meet the needs of new applications and to improve current applications. Unfortunately, these performance increases are inhibited by the degradations that result during the fabrication processes and/or result because of the structural elements included in such devices. For example, crosslinking organic semiconductor material with UV light causes the formation of dangling radicals, molecular fragments and the like that negatively impact the performance of the organic semiconductor material and the device in which the material is included. Reducing the amount of UV light used to crosslink a material leaves the material only partially crosslinked. Since the unpolymerized (uncrosslinked) material is not incorporated into the crosslinked material matrix, the unpolymerized material may be washed away by solvents used in subsequent fabrication steps and this may result in the creation of voids. These voids are randomly formed and result in non-uniform films that negatively impact the performance of the film. Similar non-uniformity problems also occur due to the inclusion of certain structural elements such as rubbed alignment layers.
[0004] Accordingly, there is a strong need in the art for fabrication processes and devices that have reduced material degradation and non-uniformities due to the organic semiconductor material or layer.
BRIEF SUMMARY OF THE INVENTION
[0005] An aspect of the present invention is to provide a method of forming a layer including mixing at least a first material and a second material to form a mixture, depositing the mixture on a surface and polymerizing the mixture to form a polymer network, the polymer network being at least one of charge-transporting or luminescent. The rate of polymerization of the mixture is greater than a rate of polymerization of the first material and the rate of polymerization of the mixture is greater than a rate of polymerization of the second material.
[0006] Another aspect of the invention is to provide a method of forming a layer including mixing at least a first material and a second material to form a mixture, depositing the mixture on a surface and polymerizing the mixture to form a polymer network, the polymer network being at least one of charge-transporting or luminescent. The amount of energy per unit of mass used for polymerizing the mixture is less than an amount of energy per unit of mass used for polymerizing of the first material and an amount of energy per unit of mass used for polymerizing of the mixture is less than an amount of energy per unit of mass used for polymerizing of the second material.
[0007] Another aspect of the invention is to provide a method of forming a layer including mixing at least a first material and a second material to form a mixture, depositing the mixture on a surface and polymerizing the mixture to form a polymer network, the polymer network being at least one of charge-transporting or luminescent. The power level used for polymerizing the mixture is less than a power level used for polymerizing of the first material and the power level used for polymerizing of the mixture is less than an a power level used for polymerizing of the second material.
[0008] Another aspect of the invention is to provide a method of forming a layer including mixing at least a first material and a second material to form a mixture, depositing the mixture on a surface and polymerizing the mixture to form a polymer network, the polymer network being at least one of charge-transporting or luminescent. The time used for polymerizing the mixture is less than a time used for polymerizing of the first material and the time used for polymerizing of the mixture is less than a time used for polymerizing of the second material.
[0009] Another aspect of the invention is to provide a method of forming a layer including mixing at least a first material and a second material to form a mixture, depositing the mixture on a surface and polymerizing the mixture to form a polymer network, the polymer network being at least one of charge-transporting or luminescent. The crosslink density of the mixture is greater than a crosslink density of the first material provided both the mixture and the first material are polymerized under the same conditions and the crosslink density of the mixture is greater than a crosslink density of the second material provided both the mixture and the second material are polymerized under the same conditions.
[0010] Another aspect of the invention is to provide a charge-transporting or luminescent layer including a mixture of at least a first and second material on an alignment layer that is unrubbed, the mixture being capable of forming a polymer network that is at least one of charge-transporting or luminescent.
[0011] Another aspect of the invention is to provide a charge-transporting or luminescent layer including a polymer network that is at least one of charge-transporting or luminescent. The polymer network is on an alignment layer that is unrubbed.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] The invention will be described in detail with reference to the following drawings in which like reference numerals refer to like elements wherein:
[0013] FIG. 1 illustrates an organic light emitting device according to the present invention.
[0014] FIG. 2 illustrates an exemplary process of fabricating the device of including one or more mixtures of reactive mesogen material that is polymerized.
[0015] FIG. 3 shows the absorption spectra of a mixture before and after crosslinking (graph line a), after washing (graph line b), and shows the PL spectrum of an insoluble liquid crystalline polymer network formed as a thin solid film after crosslinking of the mixture (graph line c).
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0016] Organic material that is able to be aligned on a molecular basis may be deposited on a substrate or other surface and then crosslinked to form a crosslinked polymer network. By using a mixture of polymerizable (crosslinkable) materials instead of a single polymerizable material, the rate of polymerisation may be increased. This increased polymerization rate facilitates room temperature fabrication in much shorter times and with much less energy being applied. This decrease in the energy being applied into the organic material decreases the amount of degradation produced by the polymerization process. Additionally, the use of a mixture may also improve the crosslinking density, may improve the quality or uniformity of alignment, and may improve the uniformity of the crosslinked polymer network.
[0017] For example, solvent solutions of binary or other mixtures of charge-transporting and/or light-emitting reactive mesogens with liquid crystalline phases (e.g., nematic or smectic phases) may be spin coated on a conducting photoalignment layer. The spin coating may be done at room temperature to form a film of liquid crystal either in a liquid crystalline phase that is thermodynamically stable at room temperature or in a super cooled liquid crystalline phase below its normal solid to liquid crystal phase transition temperature. Mixtures with thermodynamically stable liquid crystalline phases at room temperature have the advantage of lower viscosity and subsequent ease of crosslinking polymerization. The photoalignment layer aligns the reactive mesogen mixtures at room temperature on the substrate surface with the liquid crystalline director in the plane of the substrate such that one or more monodomains with planar orientation is formed. The charge injection and transport in the crosslinked polymer network is facilitated by the planar orientation. The presence of many different domains does not impair the charge injection and transport of the layers or the emission properties of devices containing such layers. The photoalignment layer may be irradiated by plane polarized UV light to create uniformly anisotropic surface energy at the layer surface. When the reactive mesogen mixture is subsequently coated on the photoalignment layer, the mixture and subsequent polymer network produced on crosslinking have a macroscopic monodomain. Additionally, the polymer network is insoluble and intractable which allows further layers with a different function to be deposited subsequently in a similar fashion.
[0018] The photoalignment layer may be used to align a layer of a mixture of reactive mesogens that becomes a polymeric hole transport layer with liquid crystalline order capon subsequent solvent casting on the photoalignment layer and crosslinking by exposure to UV radiation. Then a second layer of a mixture of reactive mesogens may be solvent cast on top of the hole transport layer. This second layer is aligned into a liquid crystalline monodomain by interaction with the aligned surface of the hole transport layer. The alignment of the second layer is believed to be achieved by molecular interactions between the molecules of the reactive mesogen materials at the interface between the two layers. The second reactive mesogen monolayer may now be crosslinked by exposure to UV radiation to form a polymeric emitter layer. Thus a series of organic semiconductor layers with liquid crystalline order may be built up with all of the molecular cores of the polymers oriented in the same direction.
[0019] For example, FIG. 1 illustrates an organic light emitting device 100 according to the present invention that includes a hole injection layer 102 , hole transport layer 104 , an emitter 106 , an electron transport layer 108 , an electron injection layer 110 , and charge carrier blocker layers 112 may be produced one layer at a time with all of the layers having mutually aligned liquid crystalline order. The device may be fabricated on a suitable alignment layer 114 and may include substrates and other elements not shown. Alternatively, some of these layers (including the alignment layer) may be omitted, a subset of adjacent layers may be built up according to this method, or subset of adjacent layers may be built up according to this method with some of the layers (including the alignment layer) being omitted.
[0020] FIG. 2 illustrates an exemplary process 200 of fabricating the device including one or more mixtures of reactive mesogen material that is polymerized. The process, 200 begins with the initial fabrication steps of the device including forming an alignment layer 202 . The next step 204 is applying a mixture to the alignment layer followed by the polymerization of the mixture step 206 . If there are no additional layers to be formed from a mixture, the final step 208 of completing the device is performed. If there are additional layers, the next step 210 of applying the next mixture to the polymerized mixture is performed followed by the polymerization of the just applied mixture step 210 . If there are no additional layers to be formed from a mixture, the final step 208 of completing the device is performed. If there are additional layers, the last two steps 210 , 212 are repeated.
[0021] If the polymerization process does not need an initiator, such as a photoinitiator, there will be no unreacted initiators to quench emission or degrade the performance and lifetime. For example, ionic photoinitiators may act as impurities in finished electronic devices and degrade the performance and lifetime of the devices.
[0022] Any suitable conducting photoalignment layer may be used. For example, the photoalignment layers described in US 2003/0021913 may be used. Alternatively, alignment may be achieved by any other suitable alignment layer or may be achieved without an alignment layer (e.g., the application of electric or magnetic fields, the application of thermal gradients or shear, surface topology, another suitable alignment technique or the combination of two or more techniques). However, rubbed alignment layers are not suitable for organic semiconductor layers and elements, such as the emitter layer in an organic light emitting device or semiconductor layers in integrated circuitry, because the organic layers and elements in such devices are thinner than the amplitude of the surface striations produced in alignment layers by rubbing. In some cases, the roughness resulting from the rubbing process has a thickness on the order of the thickness of the organic layers and elements. Additionally, diverse alignments may be imparted by an alignment layer(s) or technique(s). These diverse alignments may be in a pattern suitable for use in a pixelated device.
[0023] The crosslinking density of a network formed from a mixture of polymerizable monomers is higher than that of a network formed by the polymerization of the corresponding individual monomers. The increased crosslinking density may result because in formulating a mixture the solid to liquid crystal transition temperature is depressed below that of any of the individual components and may be depressed below room temperature. This means that the mixture has a thermodynamically stable liquid crystalline phase at room temperature and, as a result, has considerably reduced viscosity as compared to the super cooled glassy liquid crystalline phases of the individual components. This in turn means that reactive mesogen molecules are more mobile within the room temperature phase and thus are able to more quickly and more easily orient themselves to initiate the crosslinking reactions. Such anisotropic polymer network having a higher crosslinking density improves the performance of devices including layers, films or elements fabricated from the network and results in more stable devices.
EXAMPLE 1
[0024] A binary mixture of 2,7-bis{4-[7-(1-vinylallyloxycarbonyl)heptyloxy]-4′-biphenyl}-9,9-dioctylfluorene mixed with 2,7-bis {4-[10-(1-vinylallyloxycarbonyl)decyloxy]-4′-biphenyl}-9,9-dioctylfluorene in a ratio of 1:3 (the mixture (mixture 1) has a low melting point (Cr—N=22° C.) and a high nematic clearing point (N—I=75° C.)) is coated on a quartz substrate and irradiated with unpolarised UV radiation from an argon ion laser. The laser emits 325 nm UV light and has a total fluence of 15 J cm −2 . The UV radiation causes photo polymerization of the diene end-groups without the use of a photoinitiator. The polymerization of the mixture is performed at room temperature (e.g., 25° C.) and users an order of magnitude less radiation (e.g., 200 J cm −2 ) than is needed to polymerize the mixture component 2,7-bis {4-[10-(1-vinylallyloxycarbonyl)decyloxy]-4′-biphenyl}-9,9-dioctylfluorene in the glassy nematic state at the same temperature. FIG. 3 shows the absorption spectra of the mixture after crosslinking is substantially the same as before crosslinking (graph line a) and improves after washing (graph line b). FIG. 3 shows the PL spectrum of the insoluble liquid crystalline polymer network formed as a thin solid film after crosslinking of mixture (graph line c).
EXAMPLE 2
[0025] A binary mixture of compound I, 2-(5-{4-[10-(1-vinyl-allyloxycarbonyl)-decyloxy]phenyl}thien-2-yl)-7-{4-[10-(1-vinyl-allyloxycarbonyl)decyloxy]-4′-biphenyl}-9,9-dipropylfluorene (1 part) and of compound II, 2-(5-{4-[10-(1-vinyl-allyloxycarbonyl)-decyloxy]phenyl}thien-2-yl)-7-{4-[10-(1-vinyl-allyloxycarbonyl)decyloxy]-4′-biphenyl}-9,9-dioctylfluorene (1 part) is a room temperature nematic liquid crystal mixture (mixture 2). This material may also be coated on to a quartz substrate and crosslinked with radiation from an argon ion laser as above. After crosslinking, the insoluble liquid crystalline polymer network has blue photoluminescence.
[0026] Mixture 2 has good hole transporting characteristics and may be used as a hole transporting layer in an organic light emitting device. For example, a 50 nm thick layer of mixture 2 may be cast by spin coating from chloroform on an ITO-coated glass substrate previously coated with a conductive photoalignment layer such as described in US Patent Application 2003/0099785. The room temperature nematic is homogenously aligned into a uniform layer by the photoalignment layer. Unpolarized irradiation by an argon ion laser at 325 nm with a total fluence of 15 J cm −2 may be used to crosslink the material. The irradiation may be carried out through a photomask if it is desired to pattern the hole transport layer. After exposure the layer may be washed with chloroform to remove uncrosslinked monomer.
[0027] Next a 50 nm layer of mixture 1 may be cast by spin coating from chloroform solution on top of the already fabricated hole transport layer fabricated from mixture 2. The room temperature nematic material of mixture 2 is homogenously aligned by intermolecular interactions at its interface with the hole transport layer. The nematic mixture 2 layer is irradiated with unpolarised 325 nm. UV radiation from an argon ion laser with a total fluence of 15 J cm −2 . This irradiation may also be carried out through a photomask to form a patterned emitter layer. As was described in US Patent Application 2003/0119936, the resulting multilayer assembly may be further assembled into a working organic light emitting device by vapor deposition of aluminum electrodes and hermetic packaging of the device.
[0028] The synthesis of the materials in mixture 1 is described in US Patent Application 2003/0119936, which is incorporated herein in its entirety by reference. Similar synthetic methods to those used in US Patent Application 2003/0119936 may be used to prepare compounds I and Il. The synthetic route used may be as follows:
where n=3, m=10 for compound I and n=8, m 10 for compound II.
[0030] The materials of the mixture that are polymerized to form the polymer network may be made from any suitable material. For example, such materials include those suitable reactive mesogens having the general structure B-S-A-S-B wherein A is a chromophore, an aromatic molecular core, a heteroaromatic molecular core, or a rigid molecular core with conjugated pi-electron bonds, S is a spacer and B is an endgroup susceptible to radical polymerisation. Exemplary endgroups B include photopolymerisable non-conjugated diene groups such as a 1,4-pentadien-3-yl group, a 1,6-heptadien-4-yl group or a diallylamino group.
EXAMPLE 3
[0031] Another exemplary embodiment is a stereoscopic display device fabricated as in Example 2 except the photoalignment layer includes a portion having a first alignment direction and a second alignment direction that is orthogonal to the first alignment direction. This results in an emitter layer that produces light of two different polarizations. If a viewer is wearing a pair of goggles or glasses with one eye viewing light of one polarization and the other eye viewing light of the orthogonal polarization, the viewer will be able to see a stereoscopic image. The goggles or glasses or other suitable eyewear may include simple polarizing lenses if the differently polarized areas of the display device are separately actuated or otherwise caused to separately emit light to the viewer (e.g., individual pixels corresponding to the differently aligned portions). Otherwise, the goggles or glasses or other suitable eyewear may include shutters, such as liquid crystal display shutters, that provided a time multiplexed image to the viewer so as to allow the differently aligned portions of a pixel to be actuated together. Alternatively, other suitable stereoscopic configurations may be used.
[0032] The mixtures of the present invention may be incorporated as anisotropic polymer networks in organic light-emitting devices. The polymer networks may be formed by polymerising mixtures of charge-transporting and/or light-emitting reactive mesogens. Such devices also may include a conducting photoalignment layer and when used in displays may be addressed with active or passive matrix addressing. The display devices may be monochrome or multicolor, and may be pixelated or unpixelated. The devices may have polarized emissions produced by emissive layers comprising the anisotropic polymer networks. The polarized light emitting devices may be used as monochrome or multicolor backlights (e.g., liquid crystal display backlights). Such organic light-emitting devices may incorporate anisotropic polymer networks as emissive layer or elements and may include luminescent dyes (e.g., pleochroic dyes). These polymer networks also may be security devices or stereoscopic displays.
[0033] The processes and devices disclosed herein are suitable for application to electronic devices, semiconductor devices, organic light emitting devices, and other devices. Exemplary applications include transistors such as FETs, transistor arrays such as those useful for addressing matrix displays, integrated electronic circuitry, mobile telephones, digital cameras, hand held computers, watches, clocks, game machines, and other consumer electronic goods.
[0034] Although several embodiments of the present invention and its advantages have been described in detail, it should be understood that changes, substitutions, transformations, modifications, variations, permutations and alterations may be made therein without departing from the teachings of the present invention, the spirit and the scope of the invention being set forth by the appended claims. | A method of forming a layer including mixing at least a first material and a second material to form a mixture, depositing the mixture on a surface, and polymerizing the mixture to form a polymer network. The polymer network being at least one of charge-transporting or luminescent has improved properties as compared to the first and second materials including the rate of polymerization, the power level, time, and/or amount of energy per unit of mass used for polymerizing. The polymer network may be formed on an alignment layer that is unrubbed such as a photoalignment layer. The polymer network may be fabricated with uniform structure and thickness. The polymer network may have a liquid crystal phase and includes few dangling radicals and molecular fragments. | 2 |
RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional Patent Application Nos. 61/602,417 and 61/602,409, both filed on Feb. 23, 2012, both of which are incorporated herein in their entirety by reference thereto.
BACKGROUND
[0002] 1. Field of the Disclosure
[0003] This disclosure relates to a process for free radical and for living or controlled polymerization of alkene monomers (e.g., fluorine substituted alkene monomers), particularly the use of hypervalent iodide (HVI) radical initiators in the living or controlled polymerization of alkene monomers and for the functionalization of (organic) substrates with the CF 3 or RF groups.
[0004] 2. Discussion of the Background Art
[0005] Conventional chain polymerization of vinyl monomers usually consists of three main elemental reaction steps: initiation, propagation, and termination. Initiation stage involves creation of an active center from an initiator. Propagation involves growth of the polymer chain by sequential addition of monomer to the active center. Termination (including irreversible chain transfer) refers to termination of the growth of the polymer chain. Owing to the presence of termination and poorly controlled transfer reactions, conventional chain polymerization typically yields a poorly controlled polymer in terms of molecular weight and polydispersity which control the polymer properties. Moreover, conventional chain polymerization processes mostly result in polymers with simple architectures such as linear homopolymer and linear random copolymer.
[0006] Living polymerization is characterized by the absence of any kinds of termination or side reactions which might break propagation reactions. The most important feature of living polymerization is that one may control the polymerization process to design the molecular structural parameters of the polymer. Additional polymerization systems where the termination reactions are, while still present, negligible compared to propagation reaction are known in the art. As structural control can generally still be well achieved with such processes, they are thus often termed “living” or controlled polymerization.
[0007] In living or controlled polymerization, as only initiation and propagation mainly contribute to the formation of polymer, molecular weight can be predetermined by means of the ratio of consumed monomer to the concentration of the initiator used and will increase linearly with conversion. The ratio of weight average molecular weight to number average molecular weight, i.e., molecular weight distribution (Mw/Mn), may accordingly be as low as 1.0, and the polymers have well defined chain ends. Moreover, polymers with specifically desired structures and architectures can be purposely produced. In terms of topology, such structures and architectures may include linear, star, comb, hyperbranched, dendritic, cyclic, network, and the like. In terms of sequence/composition distribution, such structures and architectures may include homopolymer, random copolymer, block copolymer, graft copolymer, gradient copolymer, tapered copolymer, periodic copolymer, alternating copolymer, and the like. In terms of functionalization, such structures and architectures may include telechlics, macromonomer, labeled polymer, and the like.
[0008] Living polymerization processes have been successfully used to produce numerous polymeric materials which have been found to be useful in many applications. However, many living polymerization processes have not found wide acceptance in industrial commercialization, mainly due to high cost to industrially implement these processes. Thus, searching for practical living polymerization processes is a challenge in the field of polymer chemistry and materials.
[0009] Additionally, as (co)polymers of main chain fluorinated monomers (e.g., vinylidene fluoride (VDF), hexafluoropropene, tetrafluoroethylene, trifluorochloroethylene, and the like) are industrially significant, the study of their controlled radical polymerization and the synthesis of complex polymer architectures thereby derived, would be desirable. However, such polymerizations are challenging on laboratory scale, as bp VDF =−83° C. Thus, telo/polymerizations are carried out at T>80-150° C. and require high-pressure metal reactors.
[0010] Kinetic studies of VDF polymerizations involve many one-data-point experiments as direct sampling is difficult. This is very time-consuming and expensive due to the typical lab unavailability of a large number of costly metal reactors, which moreover require tens of grams of monomer. The development of methods that would allow small scale (e.g., a few grams) VDF polymerizations at ambient temperature in inexpensive, low pressure glass tubes, would be highly desirable, since the methods could easily be adapted for fast screening of a wide range of polymerization and of reaction conditions, and could also take advantage of photochemistry. The development of such methods would also be useful on a large scale, for example, in an industrial setting. Conventional initiating systems such as peroxides or redox systems do not initiate the polymerization of VDF at ambient or room temperature.
[0011] Driven by the unique properties imparted by the —CF 3 moiety onto chemical structures ranging anywhere from synthetic drugs to polymers and nanostructures, trifluoromethylation (TFM) has recently emerged as a very valuable technique towards improving and expanding molecular properties and functions.
[0012] As such, while the vast majority of TFM reactions involve nucleophilic (“CF 3 − ” e.g., Me 3 Si—CF 3 ), electrophilic (“CF 3 + ” e.g. chalcogen salts [CF 3 —YAr 2 ]OTf, Y═O, S, Se, Te, or cyclic iodanes such as 1-trifluoromethyl-1,2-benziodoxole, CF 3 —I(-Ph-OCO—) as well as organometallic (e.g., “CF 3 —Cu”, or Pd, Ni) protocols for arene or carbonyl TFM functionalization, very recently, radical (CF 3 .) aryl (CF 3 SO 2 Na/ t BuOOH), enantioselective carbonyl (CF 3 I/RuCl 2 (PPH 3 ) 3 ) as well as photomediated aryl (Ru(phen) 3 Cl 2 /CF 3 SO 2 Cl) and carbonyl (CF 3 —I) α-TFMs have emerged as a much more/very convenient/inexpensive/very powerful strategies for the rapid synthesis of TFM-lated libraries with wide structural diversity.
[0013] Conversely, fluorinated (co)polymers derived from radical reactions are a fundamental class of specialty materials endowed with a wide range of high-end applications which require their precise synthesis. However, while modern state-of-the-art controlled radical polymerizations (CRP) methods (atom transfer, nitroxide or reversible addition-fragmentation) have undergone remarkable developments for conventional monomers such as (meth)acrylates or styrene, they remain ineffective for the highly reactive, gaseous main chain fluorinated alkene monomers (FMs: vinylidene fluoride (VDF), hexafluoropropene (HFP), tetrafluoroethylene, etc).
[0014] Thus, due to the current lack of suitable CRP chemistry, the synthesis, characterization and fundamental understanding of the self-assembly, properties and applications of well-defined FM complex macromolecular architectures (blocks, graft, hyperbranched, stars, etc.) still lag significantly behind those associated with the corresponding materials derived from conventional alkenes (styrene, acrylates, dienes, etc.).
[0015] To date, industrial FM-CRP is still accomplished with the oldest of CRP methods, theiodine degenerative transfer (IDT: P n .+P m —I P n —I+P m .), which evolved from high temperature (100-250° C.) free radical VDF telomerizations with polyhalides, and especially (per)fluorinated iodine (R F —I) chain transfer (CT) agents, including CF 3 —I or I—(CF 2 ) n —I.
[0016] However, while the R F —I derived electrophilic R F . radicals add readily to nonfluorinated alkenes at room temperature (rt) under metal catalysis, and many metal complexes activate typical alkyl halide (R—X) ATRP initiators,only very low VDF oligomers are obtained, even at T>100° C. from transition metal salts and polyhalides. Moreover, although VDF polymerization can proceed at room temperature (rt), the metal mediated radical initiation of such electrophilic FMs directly from halides and thus metal-mediated FM-CRP at T<100° C., including around rt, is not available. Consequently, conventional FM-IDT always demands a free radical initiator (e.g. t butyl peroxide).
[0017] As such, the development of FM-CRP, the synthesis of elaborate FM polymer architectures, and the mapping the resulting fluoromaterials genome remains a worthy endeavor. Conversely, such polymerizations are very challenging especially in an academic laboratory scale/setting, as all FMs are gases (b p VDF =−83° C.) and typical telo/polymerizations are carried out at T>100-200° C., in expensive, high-pressure metal reactors.
[0018] Moreover, in additional contrast with acrylates- or styrene-CRP, VDF-IDT generates two halide chain ends, P n —CH 2 —CF 2 —I and P m —CF 2 —CH 2 —I with vastly different reactivity, and, while acrylate or styrene kinetics can effortlessly be sampled even on a 1 g scale, FM polymerizations involve many time-consuming one-data-point reactions using at least tens of grams of monomer.
[0019] Thus, development of mild temperature protocols for low pressure, small-scale polymerizations in inexpensive glass tubes, would be very appropriate for fast catalyst and reaction condition screening and also amenable to photochemistry. As such, while VDF high power UV telomerizations exist, until recently, there were no reports on VDF polymerizations under regular visible light.
[0020] While CH 3 . is also available from, for example, the decomposition of TBPO, the generation of CF 3 . from CF 3 —I is expensive and impractical (b p CF3I =−22.5° C.). In fact, except for Mn 2 (CO) 10 experiments above, very few other CF 3 . precursors have ever been evaluated in the initiation of FMs, where such radicals were generated either by high temperature thermolysis or under strong UV irradiation from commercially available but inconvenient and expensive CF 3 —Br and CF 3 —I, or from commercially unavailable CF 3 —SO 2 —SR, CF 3 —S—(C═S)—OR, explosive CF 3 —C(O)O—O(O)C—CF 3 , toxic Hg(CF 3 ) 2 , Cd(CF 3 ) 2 , Te(CF 3 ) 2 , or from even more exotic and expensive substrates such as CF 3 -decorated octafluoro[2.2]paracyclophane or persistent perfluoro-3-ethyl-2,4-dimethyl-3-pentyl radicals. Thus, availability of a clean, safe, nongaseous, commercially available and inexpensive source of CF 3 . radicals would be highly desirable for TFM radical reactions involving either polymerizations or arene functionalization.
[0021] Interestingly, although known for over a century, hypervalent iodine (III,V) (HVI) derivatives (λ 3 - and λ 5 -iodanes) have recently undergone a resurgence in organic chemistry. Consequently, they have also become inexpensively commercially available, as illustrated especially by acyloxyiodobenzenes such as (CX 3 COO) 2 I III Ph, (X═H, I-DAB, X═F, I-FDAB) and (CH 3 COO) 3 I V (-Ph-CO—O—) (Dess-Martin cyclic periodinane, DMP,), or to a lesser extent, by diaryliodonium salts (Ar 2 I + Y − , Y═PF 6 , OTf, etc.
[0022] While the overwhelming majority of such HVI carboxylates applications are oxidations, examples of radical processes are also emerging. Thus, alkyl radicals obtained thermally or under Hg—UV from the decarboxylation of HVIs derived in-situ by ligand exchange of IDAB and IFAB with carboxylic acids, add to alkenes or alkylate heteroaromatic bases. Alternatively, in the additional presence of I 2 , HVIs mediate the hypoiodite reaction of R—Y—H such as alcohols, carboxylic acids, and amines to generate transient R—Y—I, which upon UV-VIS irradiation provide the corresponding R—Y. radicals (Y═O, COO, NR).
[0023] However, while diaryliodonium salts are known cationic polymerizations photoinitiators and photoacid generators in photolithography, the potential use IDAB and IFAB as radical polymerization initiators, remains largely ignored and, to the best of our knowledge, there are no reports on the use of IDAB and IFAB as initiators for the radical polymerization of fluorinated monomers, on the use of IFAB in trifluoromethylation reactions, and on the photolysis of DMPI and its radical reactions.
[0024] It would be desirable to provide a method for living polymerization of alkene and fluoroalkene monomers which provides a high level of macromolecular control over the polymerization process and which leads to uniform and more controllable polymeric products. It would be especially desirable to provide such a living polymerization process with existing facility, and which enables the use of a wide variety of readily available starting materials. It would be further desirable to provide a method that would allow small scale (e.g., a few grams) VDF polymerizations at ambient temperature in inexpensive, low pressure glass tubes, and also large scale VDF polymerizations, for example, in industrial settings. The glass tubes as well as metal reactors could also take advantage of photochemistry.
[0025] The present disclosure also provides many additional advantages, which shall become apparent as described below.
SUMMARY OF THE DISCLOSURE
[0026] This disclosure addresses the problems above. Milder means of radical generation and have been developed including examples of transition metal mediated, controlled, and respectively free radical VDF polymerizations (VDF-IDT-CRP and VDF-FRP), carried out at 40° C. in low pressure glass tubes, and using a Mn 2 (CO) 10 visible light photocatalyst in conjunction with perfluoroalkyl iodides and respectively, with a wide variety of other alkyl halides. Moreover, the complete activation of both P n —CH 2 —CF 2 —I and P m —CF 2 —CH 2 —I PVDF chain ends has been demonstrated, towards the synthesis of well-defined PVDF block copolymers, as described in copending U.S. Provisional Patent Application Ser. No. 61/602,409, supra.
[0027] Mn 2 (CO) 10 experiments have been conducted that reveal that since VDF is a very reactive monomer, only highly reactive radicals such as R F . or CX 3 . (X═H, F, Cl) were capable of rt initiation. Thus, although many halides were tested, the only effective initiators were R F —X or X—R F —X (X═Cl, Br, I) and respectively CH 3 —I, CF 3 —I, CF 3 —SO 2 —Cl, CCl 4 and CCl 3 Br, where CF 3 —I and CF 3 —SO 2 —Cl also provided examples of Mn 2 (CO) 10 -catalyzed alkene TFM, as described in copending U.S. Provisional Patent Application Ser. No. 61/602,409, supra.
[0028] In accordance with this disclosure, for radical chemistry applications, carboxylate HVIs are protected synthetic equivalents of their unstable/explosive corresponding diacylperoxides, where R F . or CX 3 . radicals, inaccessible via R F /CX 3 —CO—O—O—CO—CX 3 /R F , become readily available via rt photolysis of the stable, corresponding R F /CX 3 —CO—O—I(Ph)-O—CO—CX 3 /R F or Ph(COO)I(OCOCX 3 /R F ) 3 HVI derivatives. Moreover, any such HVIs can also be generated in situ from R F /CX 3 COOH and catalytic PhI using Oxone. Thus while typical room temperature free radical azo or peroxide initiators are expensive, hazardous and require refrigeration, the analogous HVI carboxylates are much more stable and convenient.
[0029] HVIs carboxylates are a new class of initiators for the rt FRP of alkene monomers, and, in conjunction with the appropriate mediators, of the corresponding controlled radical polymerizations. IFAB as the least expensive and most convenient source of CF 3 . and of CF 3 I. In an embodiment, IFAB is useful as a TFM agent using the more difficult VDF as a model monomer, in a metal free, organocatalysis of FM-CRP.
[0030] This disclosure provides novel radical trifluromethylations with the (CF 3 COO) 2 I III Ph. In accordance with this disclosure, commercially available [bis(acyloxy)iodo]arenes ((CX 3 COO) 2 I III Ph and the Dess Martin-(CX 3 COO) 3 IPh are useful as initiators for the polymerization of VDF at mild temperatures. This discosure also involves R F . or R. that can also be derived from the rt photolysis of novel VDF initiators such as hypervalent iodides (HVIs, (CF 3 /CH 3 COO) 2 IPh′ eq. 3). In accordance with this disclosure, a much more convenient CX 3 . source can be provided by inexpensive, commercially available hypervalent iodides (I III ) (HVI—X, X═H, F) such as (CX 3 COO) 2 IPh or the Dess-Martin reagent. FHVI can be used as the cheapest for both radical trifluoromethylation of various substrates, as well as trifluoromethyl initiation of radical polymeriztions.
[0031] This disclosure relates in part to a process comprising polymerizing at least one unsaturated monomer, e.g., alkene monomer, in the presence of a hypervalent iodide radical initiator and optionally a solvent. The process is conducted under reaction conditions and for a time sufficient to polymerize the at least one unsaturated monomer to form a polymer.
[0032] This disclosure also relates in part to a process comprising polymerizing at least one unsaturated monomer, e.g., alkene monomer, in the presence of a hypervalent iodide radical initiator, a solvent, and an iodine source. The process is conducted under reaction conditions and for a time sufficient to controllably polymerize the at least one unsaturated monomer to form a polymer.
[0033] This disclosure further relates in part to a process comprising providing an iodide terminated polymer; converting the iodide terminated polymer to a hypervalent iodide radical initiator; and polymerizing at least one unsaturated monomer, e.g., alkene monomer, in the presence of the hypervalent iodide radical initiator, an optional catalyst and a solvent. The process is conducted under reaction conditions and for a time sufficient to polymerize the at least one unsaturated monomer to form a block polymer.
[0034] This disclosure yet further relates in part to polymers, random copolymers and block copolymers produced by the above described processes.
[0035] The disclosure describes hypervalent iodide radical initiators for the room temperature radical thermal and photochemical polymerization of alkenes, and especially fluorine substituted alkenes. The radical thermal and photopolymerization can also be carried out at higher or lower temperatures than room temperature. The present disclosure provides a method for living polymerization of alkene monomers, which provides a high level of macromolecular control over the polymerization process and which leads to uniform and controllable polymeric products. Hypervalent iodide derivatives are a unique methodology to achieve initiation of the polymerization process, either thermally or preferably under visible or ultraviolet initiation.
[0036] Further objects, features and advantages of the present disclosure will be understood by reference to the following drawings and detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
[0037] FIG. 1 depicts a generalized mechanism for polymerization of vinylidene fluoride (VDF) initiated from (CR 3 COO) 2 I-Ph.
[0038] FIG. 2 graphically depicts the dependence of Mn and Mw/Mn on conversion in the VDF polymerization initiated from (CF 3 COO) 2 I-Ph and using I 2 and CHI 3 as iodine sources.
[0039] FIG. 3 graphically depicts the dependence of Mn and Mw/Mn on conversion in the VDF polymerization initiated from (CF 3 COO) 2 I-Ph and using I 2 . FIG. 3 also explains the analogy between VDF/RI/(CF 3 COO) 2 I-Ph=VDF/CF 3 I/(CF 3 COO) 2 I-Ph.
[0040] FIG. 4 graphically depicts the dependence of Mn and Mw/Mn on conversion in the VDF polymerizations initiated from (CF 3 COO) 2 I-Ph and using I(CF 2 ) 6 I.
[0041] FIG. 5 graphically depicts the dependence of the nature of the PVDF-I chain ends on conversion, and demonstrates that the polymers made herein are adequate for block copolymer synthesis.
[0042] FIG. 6 sets forth the characterization of selected examples of PVDF-I polymers synthesized using hypervalent iodides and various iodine sources in accordance with Example 7.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0043] As used herein, the term “polymerization” includes oligomerization, cooligomerization, polymerization and copolymerization. The copolymerization can be block or random.
[0044] As used herein, the term “polymer” includes oligomer, cooligomer, polymer and copolymer. The copolymer can be block or random.
[0045] As used herein, the term “hydrocarbon” includes any permissible group containing carbon and hydrogen atoms, in particular, groups or substituents having from about 1 to about 24 or more carbon atoms. The hydrocarbon can be substituted (e.g., fluorohydrocarbon) or unsubstituted. As used herein, . refers to a radical.
[0046] As used herein, the term “polymer” includes molecules of varying sizes having at least two repeating units. Most generally polymers include copolymers which may in turn include random or block copolymers. Specifically, “polymer” includes oligomers (molecules having from 2-10 repeating units). Polymers formed using the disclosure have varying degrees of polymerization (number of monomer units attached together), for example from 2-10; 11-25; 26-100; 101-250; 251-500; 501-750; 751-1000; 1,000-2,000; and even larger; and all individual values and ranges and sub-ranges therein, and other degrees of polymerization. As known in the art, the degree of polymerization can be modified by changing polymerizing conditions.
[0047] As known in the art, there are different measures of molecular weight of polymers: average molecular weight (M w , the weight-average molecular weight, or M n , the number-average molecular weight) and molecular weight distribution (M w /M n , a measure of polydispersity because M w emphasizes the heavier chains, while M n emphasizes the lighter ones). The number average molecular weight is the average of the molecular weights of the individual polymers in a sample. The number average molecular weight is determined by measuring the molecular weight of n polymer molecules, summing the weights, and dividing by n. The weight average molecular weight (M w ) is calculated by
[0000]
M
_
w
=
∑
i
N
i
M
i
2
∑
i
N
i
M
i
[0000] where N i is the number of molecules of molecular weight M i . The polydispersity index (PDI) is a measure of the distribution of molecular weights of the polymer and is the weight average molecular weight divided by the number average molecular weight. As the chains approach uniform chain length, the PDI approaches 1. The degree of polymerization is the total molecular weight of the polymer divided by the molecular weight of the monomer and is a measure of the number of repeat units in an average polymer chain. As described elsewhere herein, the average molecular weights of the polymers produced can vary, depending on the polymerizing conditions, and other factors, as known in the art.
[0048] As used herein, “initiators” are those substances which act spontaneously or can be activated with light or heat to initiate polymerization of the alkene monomer. Examples of initiators include hypervalent iodide radical initiators. Some initiators are activated by irradiation with light. Light used in the disclosure includes any wavelength and power capable of initiating polymerization. Preferred wavelengths of light include ultraviolet or visible. Any suitable source may be used, including laser sources. The source may be broadband or narrowband, or a combination. The light source may provide continuous or pulsed light during the process.
[0049] As used herein, “polymerizing conditions” are the temperature, pressure and the presence of an initiator that result in a detectable amount of polymer formation. Useful temperatures for polymerization are easily determined by one of ordinary skill in the art without undue experimentation in further view of the description herein. Ambient temperature may be used. In industrial use, a temperature of between about 50° C. and 100° C. is particularly useful since reaction heat can be removed easily. One example of polymerizing conditions is a temperature below the temperature at which the initiator ordinarily decomposes. Useful pressures for polymerization are readily determined by one of ordinary skill in the art without undue experimentation in further view of descriptions herein. Ambient atmospheric pressure may be used. It is known that polymerizing conditions can vary depending on the desired product. Any combination of pressure and temperature which produce a detectable amount of polymer can be used in the methods described here.
[0050] According to the present disclosure, a polymerization process is described for conducting polymerization of monomers, particularly “living” polymerization of alkenes, wherein a unique initiator, i.e., hypervalent iodide radical initiator, is provided for producing oligomers and polymers with controlled structure. In the context of the present disclosure, the term “living” refers to the ability to produce a product having one or more properties which are reasonably close to their predicted value. The polymerization is said to be “living” if the resulting number average molecular weight is close to the predicted molecular weight based on the ratio of the concentration of the consumed monomer to the initiator; e.g., within an order of magnitude, preferably within a factor of five, more preferably within a factor of 3, and most preferably within a factor of two, and to produce a product having narrow molecular weight distribution as defined by the ratio of weight average molecular weight to number molecular weight (MWD); e.g., less than 10, preferably less than 2, more preferably less than 1.5, most preferably less than 1.3.
[0051] The hypervalent iodide radical initiators useful in this disclosure can be classified based on the number of carbon ligands on the central iodine. lodinanes include 1C bonds (iodosyl/iodoso compounds (RIO) and their derivatives (RIX 2 where X is non-carbon ligand and R is aryl or CF 3 ), 2C bonds (iodonium salts (R 2 I + X − ), and 3C bonds (iodanes with 3 C—I bonds are thermally unstable and not synthetically useful). Periodinanes include 1C bond (iodyl/iodoxy compounds (RIO 2 ) and their derivatives (RIX 4 or RIX 2 O), and 2C bonds (iodyl salts (R 2 IO + X − ). An illustrative periodinane is Dess-Martin periodinane (1,1,1-triacetoxy-1,1-dihydro-1,2-benziodoxol-3(1H)-one).
[0052] Other hypervalent iodide radical initiators useful in this disclosure include compounds with more than one formal carbon bond to iodine. Such initiators include alkenyliodonium (PhI + C═CHR X − ) and alkynyliodonium (PhI + C≡CHR X − ) salts, and iodonium ylides (PhI═CXY where X and Y are electron acceptors).
[0053] Cyclic iodinanes are hypervalent iodide radical initiators useful in this disclosure. Such initiators include λ 3 -iodinanes (benziodoxazoles based on o-iodosobenzoic acid) and λ 5 -iodinanes (benziodoxazoles based on o-iodoxybenzoic acid). An illustrative cyclic iodinane is Dess-Martin periodinane (1,1,1-triacetoxy-1,1-dihydro-1,2-benziodoxol-3(1H)-one).
[0054] μ-Oxo-bridged iodanes are hypervalent iodide radical initiators useful in this disclosure. Such initiators include PhI═(X)OI(X)Ph where X is OTf, ClO 4 , BF 4 , PF 6 or SbF 6 .
[0055] The hypervalent iodide radical initiators useful in this disclosure include, for example, [bis(trifluoroacetoxy)iodo]benzene, [bis(trifluoroacetoxy)iodo]pentafluorobenzene, [bis(acetoxy)iodo]benzene, and the Dess-Martin periodinane (1,1,1-triacetoxy-1,1-dihydro-1,2-benziodoxol-3(1H)-one). The amount of hypervalent iodide radical initiator useful in the process of this disclosure is dependent on the amount of polymerizable monomer or monomers used. The polymerizable monomer or monomers can be used in a total amount of generally from 3-20,000 moles, preferably 5-2,000 moles, more preferably 10-1,000 moles per mole of the hypervalent iodide radical initiator.
[0056] Hypervalent iodides (HVI) can be derived by ligand exchange with RCOOH, or can be made in situ using catalytic PhI with an oxidant like oxone. Also, HVI exchanges with a variety of RYH (Y═N, O, etc.) and generates in situ other radicals that can be used for initiation. Perfluorinated iodides (RFIs) can be used as chain transfer agents.
[0057] Unless PVDF-derived HVI-like iodonium compounds are able to mediate degenerative transfer, an iodine source (R F /R H —I/I 2 /metal iodide, etc), is necessary for control, e.g., controlled polymerizations obtained using (CF 3 COO) 2 IPh and R F —I, (e.g., I—(CF 2 ) n —I), I 2 or RI (CHI 3 , CI 4 , allyl iodide, CN—CH 2 I, benzyl iodide, N-iodosuccinimide, Bu 3 SnI, Me 2 SnI 2 , Bu 4 NI, Ph 4 PI) or MtI (GeI 4 , PbI 4 , NaI, KI, LiI, BiI 3 , CsI, CsI 3 , InI 3 etc.) the like.
[0058] Illustrative iodine sources useful in the process of this disclosure include, for example, I 2 , CHI 3 , CI 4 , GeI 4 , PbI 4 , benzyl iodide, N-iodosuccinimide, GeI 4 ,PbI 4 , NaI, KI, LiI, BiI 3 , CsI, CsI 3 , InI 3 , Bu 3 SnI, Me 2 SnI 2 , Bu 4 NI, Ph 4 PI, and the like as well as perfluorinated iodide chain transfer agents such as I(CF 2 ) 6 I. The iodine sources can be used in amounts sufficient to provide a controlled polymerization according to the iodine degenerative transfer mechanism. Example 3 hereinbelow shows the results of photopolymerizations of VDF at 40° C. that were conducted with (CF 3 COO) 2 I-Ph. The dependence of Mn and Mw/Mn on conversion in the VDF polymerization initiated from (CF 3 COO) 2 I-Ph and using I 2 and CHI 3 as iodine sources is shown in FIG. 2 . The dependence of Mn and Mw/Mn on conversion in the VDF polymerization initiated from (CF 3 COO) 2 I-Ph, (CH 3 COO) 2 I-Ph and (CH 3 COO) 2 I(-PhCOO—) and using I(CF 2 ) 6 I as iodine source is shown in FIG. 3 . The linear dependence of Mn on conversion and narrow Mw/Mn in both figures confirm the controlled character of these polymerizations.
[0059] In the present disclosure, polymers with various specifically desired structures and architectures can be purposely produced. In terms of topology, such structures and architectures may include linear, star, comb, hyperbranched, dendritic, cyclic, network, and the like. In terms of sequence/composition distribution such structures and architectures may include homopolymer, random copolymer, block copolymer, graft copolymer, gradient copolymer, tapered copolymer, periodic copolymer, alternating copolymer, and the like.
[0060] In the present disclosure, any alkene monomers that are radically polymerizable or copolymerizable can be polymerized and/or copolymerized in the presence of the hypervalent iodide radical initiator. Illustrative alkene monomers include, for example, ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 2-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 2-methyl-1-octene, 2-ethyl-1-hexene, 5-methyl-1-heptene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 2-methyl-1-dodecene, 1-tetradecene, 2-methyl-1-tetradecene, 1-hexadecene, 2-methyl-1-hexadecene, 5-methyl-1-hexadecene, 1-octadecene, 2-methyl-1-octadecene, 1-eicosene, 2-methyl-1-eicosene, 1-docosene, 1-tetracosene, 1-hexacosene, vinylcyclohexane and 2-phenyl-1-butene, although the present disclosure is in no way limited to these examples. The alkene monomers to be polymerized by the process of the present disclosure may be linear or branched and may also contain a cycloaliphatic or aromatic ring structure. These monomers can be used singly or as admixture of two or more than two.
[0061] In a preferred embodiment, the alkene monomers are fluorine substituted alkene monomers. Illustrative fluorine substituted alkene monomers include, for example, vinylidene fluoride (VDF), hexafluoropropene, tetrafluoroethylene, trifluorochloroethylene, CF 2 ═CCl 2 , CH 2 ═CFCl, CF 2 ═CFX (where X is Cl or Br), CH 2 ═CX 2 (where X is F, Cl or Br), and CH 2 ═CHX (where X is F, Cl or Br). These monomers can be used singly or as admixture of two or more than two. Suitable alkene monomers include any permutation of alkenes with halides, e.g., halogenated alkenes having the formula CH 2 ═CHX, CH 2 ═CX 2 , CHX═CY 2 , CHX═CYX, CX 2 ═CY 2 , and CXY═CY 2 (where X and Y are independently F, Cl, Br, or I).
[0062] In accordance with this disclosure, other monomers, e.g., vinyl monomers, can be polymerized and/or copolymerized in the presence of the hypervalent iodide radical initiator. Examples of the monomers include but not limited to: carboxyl group-containing unsaturated monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, and the like (preferably methacrylic acid), C 2-8 hydroxyl alkyl esters of (meth)acrylic acid (preferably methacrylic acid) such as 2-hydroxylethyl(meth)acrylate, 2-hydroxylpropyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate and the like, monoesters between a polyether polyol (e.g., polyethylene glycol, polypropylene glycol or polybutylene glycol) and an unsaturated carboxylic acid (preferably methacrylic acid); monoethers between a polyether polyol (e.g., polyethylene glycol, polypropylene glycol or polybutylene glycol) and a hydroxyl group-containing unsaturated monomers (e.g., 2-hydroxyl methacrylate); adducts between an unsaturated carboxylic acid and a monoepoxy compound; adducts between glycidyl(meth)acrylates (preferably methacrylate) and a monobasic acid (e.g., acetic acid, propionic acid, p-t-butylbenzonic acid or a fatty acid).
[0063] Other monomers include, for example, monoesters or diesters between an acid anhydride group-containing unsaturated compounds (e.g., maleic anhydride or iraconic anhydride) and a glycol (e.g. ethylene glycol, 1,6-hexanediol or neopentyl glycol); chlorine-, bromine-, fluorine-, and hydroxyl group containing monomers such as 3-chloro-2-hydroxylpropyl(meth)acrylate (preferably methacrylate) and the like; C 1-24 alkyl esters or cycloalkyl esters of (meth)acrylic acid (preferably methacrylic acid), such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-, sec-, or t-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octylmethacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate and the like, C 2-18 alkoxyalkyl esters of (meth)acrylic acid (preferably methacrylic acid), such as methoxybutyl methacrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, ethoxybutyl methacrylate and the like; olefins or diene compounds such as ethylene, propylene, butylene, isobutene, isoprene, chloropropene, fluorine containing olefins, vinyl chloride, and the like.
[0064] Still other monomers include, for example, ring-containing unsaturated monomers such as styrene and o-, m-, p-substitution products thereof such as N,N-dimethylaminostyrene, aminostyrene, hydroxystyrene, t-butylstyrene, carboxystyrene and the like, a-methyl styrene, phenyl(meth)acrylates, nitro-containing alkyl(meth)acrylates such as N,N-dimethyl-aminoethyl methacrylate, N-t-butylaminoethyl methacrylate; 2-(dimethylamino)ethyl methacrylate, methyl chloride quaternized salt, and the like; polymerizable amides such as (meth)acrylamide, N-methyl(meth)acrylamide, 2-acryloamido-2-methyl-1-propanesulfonic acid, and the like; nitrogen-containing monomers such as 2-, 4-vinyl pyridines, 1-vinyl-2-pyrrolidone, (meth)acrylonitrile, and the like; glycidyl group-containing vinyl monomers such as glycidyl(meth)acrylates and the like, vinyl ethers, vinyl acetate, and cyclic monomers such as methyl 1,1-bicyclobutanecarboxylate. These monomers can be used singly or as admixture of two or more than two.
[0065] The unsaturated monomers useful in this disclosure may homopolymerize or copolymerize. Fluorine substituted unsaturated monomers, e.g., fluorine substituted alkene, acrylic acid and styrene derivatives, and vinyl ether monomers, are useful in this disclosure. Suitable unsaturated monomers useful in this disclosure include, for example, any permutation of alkenes with halides as well as fluorinated acrylates, styrenes, vinyl ethers, and the like.
[0066] The polymerizable monomer or monomers can be used in a total amount of generally from 3-20,000 moles, preferably 5-2,000 moles, more preferably 10-1,000 moles per mole of the hypervalent iodide radical initiator. In an embodiment, the polymerizable monomer or monomers can be used in a total amount of from 1 to about 10,000 moles per mole of the hypervalent iodide radical initiator. The molecular weight distribution of resultant polymer (defined by the ratio of weight average molecular weight to number average molecular weight) obtained from processes of the present disclosure is generally from 1.01 to 30, mostly from 1.05 to 3.0, and more preferably less than 2.0.
[0067] Various organic or inorganic functional groups can be introduced to the ends of formed polymer or copolymer. By definition, a functional group is a moiety attached to a molecule that performs a function in terms of the reactivity and/or the physical properties of the molecule bearing it. Example of functional groups include but not limited to: halogens (e.g., Cl, Br, I), hydroxyl (—OH) groups such as —CH 2 OH, —C(CH 3 ) 2 OH, —CH(OH)CH 3 , phenol and the like, thiol (—SH) groups, aldehyde (—CHO) and ketone (>C═O) groups, amine (—NH 2 ) groups, carboxylic acid and salt (—COOM) (M is H, alkali metal or ammonium), sulfonic acid and salt (—SO 3 M) (M is H, alkali metal or ammonium), amide (—CONH 2 ), crown and kryptand, substituted amine (—NR 2 ) (R is H or C 1-18 alkyl), —C═CR′, —CH═CHR′(R′ is H or alkyl or aryl or alkaryl or aralkyl or combinations thereof), —COX (X is halogen), —CH 2 N(SiR′ 3 ) 2 , —Si(OR′) 3 , —CN, —CH 2 NHCHO, —B(OR) 2 , —SO 2 Cl, —N 3 , —MgX. Functionalized polymer and copolymers including macromonomer prepared in accordance with the disclosure may be obtained by two ways: (a) one-pot synthesis using functional initiator; (b) transformation of living or preformed polymer to a desirable functional group by known organic reactions.
[0068] In an embodiment of this disclosure, a process is provided that allows the synthesis of well-defined block copolymers of VDF with many other monomers. The process comprises providing an iodide terminated polymer, converting the iodide terminated polymer to a hypervalent iodide radical initiator; and polymerizing at least one alkene monomer in the presence of the hypervalent iodide radical initiator, optionally a catalyst and a solvent, under reaction conditions and for a time sufficient to polymerize the at least one alkene monomer to form a polymer.
[0069] The iodide terminated polymer can comprise PVDF—CF 2 —CH 2 —I and/or PVDF—CH 2 —CF 2 —I, and the hypervalent iodide radical initiator can comprise PVDF—I(OOCR) 2 where R is alkyl or perfluoroalkyl. The catalyst can comprise Mn 2 (CO) 10 or Re 2 (CO) 10 . The polymerization can be conducted at room temperature under visible light or UV light. The polymers contain iodide terminal groups that which allow the synthesis of block copolymers.
[0070] In an embodiment, the iodo chain ends can be activated with manganese carbonyl (or other transition metal carbonyl known to photolyze) directly, or as described in copending U.S. Provisional Patent Application Ser. No. (0008247USP), filed on an even date herewith, which is incorporated herein in its entirety. There is no need for a hypervalent iodide radical initiator. In another embodiment, the iodine chain ends can be converted to hypervalent iodide radical initiators and they may be activated photo or thermally to make block copolymers.
[0071] Various polymerization technologies can be used to make the polymer, which include but not limited to: bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, dispersion polymerization, precipitation polymerization, template polymerization, micro-emulsion polymerization. The polymerization will work with any radically polymerizable monomer. Various solvents can be used in the polymerization. Examples of the solvents are but not limited to: carbonates, e.g., dimethyl carbonate (DMC), acetonitrile, water, aliphatic solvent, aromatic solvent, hetero-atom containing solvent, supercritical solvent (such as CO 2 ), and the like. The inventive process can typically be conducted between −80° C. and 280° C., preferably between 0° C. and 180° C., more preferably between 20° C. and 150° C., most preferably between 20° C. and 130° C. The inventive process can be conducted under a pressure from 0.1 to 50,000 kPa, preferably from 1 to 1,000 kPa. The addition order of various ingredients in according with the process of the disclosure can vary and generally do not affect the outcome of the living polymerization. Depending the expected molecular weight and other factors, polymerization time may vary from 10 seconds to 100 hours, preferably from 1 minute to 48 hours, more preferably from 10 minutes to 24 hours, most preferably from 30 minutes to 18 hours. The polymerization procedure can consist of mixing the desired monomer and the hypervalent iodide radical initiator in predetermined ratios and in appropriate solvents for a given amount of time under visible or UV irradiation.
[0072] The final polymer can be used as it is or is further purified, isolated, and stored. Purification and isolation may involve removing residual monomer, solvent, and catalyst. The purification and isolation process may vary. Examples of isolation of polymers include but not limited to precipitation, extraction, filtration, and the like. Final polymer product can also be used without further isolation such as in the form of the latex or emulsion.
[0073] Polymers prepared with the inventive process may be useful in a wide variety of applications. The examples of these applications include, but not limited to, adhesives, dispersants, surfactants, emulsifiers, elastomers, coating, painting, thermoplastic elastomers, diagnostic and supporters, engineering resins, ink components, lubricants, polymer blend components, paper additives, biomaterials, water treatment additives, cosmetics components, antistatic agents, food and beverage packaging materials, release compounding agents in pharmaceuticals applications.
[0074] In the above detailed description, the specific embodiments of this disclosure have been described in connection with its preferred embodiments. However, to the extent that the above description is specific to a particular embodiment or a particular use of this disclosure, this is intended to be illustrative only and merely provides a concise description of the exemplary embodiments. Accordingly, the disclosure is not limited to the specific embodiments described above, but rather, the disclosure includes all alternatives, modifications, and equivalents falling within the true scope of the appended claims. Various modifications and variations of this disclosure will be obvious to a worker skilled in the art and it is to be understood that such modifications and variations are to be included within the purview of this application and the spirit and scope of the claims.
EXAMPLE 1
[0075] As shown in FIG. 1 , initiation begins with the thermal or fotolytical cleavage of the HVI initiator, (in this case exemplified by the commercially available (CX 3 COO) 2 IPh where X═H or F, equation 1) which generates the CX 3 and/or the CX 3 COO radicals which add to VDF (equation 2), thereby initiating the polymerization, which can be free radical. If a living polymerization is desired, iodine sources such as R—I or R F —I or MtI where R F represents a fluorinated or semifluorinated fragment, are used (equations 3 and 4). For regular R—I such as allyl iodide or CHI 3 , or I, it is expected that the R* radical is not able to add to VDF (equation 5), whereas R F * radicals such as CF 3 —(CF 2 ) n —CF 2 * are reactive enough to add to VDF (equation 8) and also engage in the iodine degenerative process (equation 8) which mediates the liing nature of the polymerization.
[0076] Under these conditions, VDF polymerization proceeds with the formation of two types of terminal iodine chain ends, namely PVDF—CH 2 —CF 2 —I and PVDF—CF 2 —CH 2 —I. The degenerative iodine transfer process is supported mainly by the more reactive PVDF—CH 2 —CF 2 —I chain ends (equations 10-12), and proceeds with the accumulation of the less reactive PVDF—CF 2 —CH 2 —I chain ends.
[0077] Finally, a minor extent of termination via bimolecular recombination (equation 13) or chain transfer to the solvent (equations 14 and 15) is also possible.
EXAMPLE 2
[0078] While VDF initiation does occur from the very expensive perfluorinated peroxides, in accordance with this disclosure, the R F . source can be provided by inexpensive, commercially available hypervalent iodides such as (CF 3 COO) 2 IPh. Although photo/thermal radical generation from (CH 3 /CF 3 COO) 2 IPh was employed in organic chemistry or for initiating free radical polymerization (FRP), HVIs were never used with fluorinated monomerss. In accordance with this disclosure, PVDF can be obtained from (CF 3 OOC) 2 IPh at room temperature under ultraviolet (UV) or visible light irradiation, with CF 3 . initiation confirmed by NMR. HVIs thus cleanly provide an excellent model initiator for benchmark testing various Q-I iodine donors. However, unless PVDF-derived HVI-like iodonium compounds are able to mediate degenerative transfer, an iodine source (R F /R H —I/I 2 ), is necessary for control, e.g., controlled polymerizations obtained using (CF 3 COO) 2 IPh and I 2 or CHI 3 .
EXAMPLE 3
[0079] FIG. 2 graphically depicts results of the dependence of Mn and Mw/Mn on conversion in the VDF polymerization initiated from (CF 3 COO) 2 I-Ph and using I 2 and CHI 3 as iodine sources.
EXAMPLE 4
[0080] FIG. 3 graphically depicts the dependence of Mn and Mw/Mn on conversion in the VDF polymerization initiated from (CF 3 COO) 2 I-Ph and using I 2 . FIG. 3 also explains the analogy between VDF/RI/(CF 3 COO) 2 I-Ph=VDF/CF 3 I/(CF 3 COO) 2 I-Ph. Since CF 3 —I is generated in situ, (Scheme 1, eq. 4), the equivalent ratios with CF 3 —I are also included. [VDF]/[“CF 3 I”]/[(CF 3 COO) 2 IPh] (or [VDF]/[I 2 ]/[(CF 3 COO) 2 IPh]): 50/1/0.5 (▾, 50/0.5/1), 100/1/1.5 (★, 50/0.25/1), 200/1/1.5 (♦, 100/0.25/1), 500/1/0.5 (⊖, 250/0.25/0.5), 500/1/1 (◯, 250/0.25.0.75), 500/1/1.5 (, 250/0.25/1) and 1,000/1/1.5 (▴, 500/0.25/1). Also included is [VDF]/[CF 3 (CF 2 ) 3 I]/[IFAB]=200/1/0.25 (▪).
EXAMPLE 5
[0081] FIG. 4 graphically depicts the dependence of Mn and Mw/Mn on conversion in the VDF polymerizations initiated from (CF 3 COO) 2 I-Ph and using I(CF 2 ) 6 I. The effect of monomer/initiator ratio (DP, degree of polymerization) is as follows: [VDF]/[I(CF 2 ) 6 I]/[(CF 3 COO) 2 IPh]=50/1/0.25 (★); 200/1/0.25 (▪), 500/1/0.25 (∇), 500/1/1 (▾); 1,000/1/1 (♦); 2,500/1/1 ( ). The effect of initiator at constant DP is as follows: [VDF]/[I(CF 2 ) 6 I]/[(CF 3 COO) 2 IPh; (CH 3 COO) 2 IPh; (CH 3 COO) 3 I(-PhCOO—)]=200/1/0.25 (▪), 200/1/0.5 (▴) and 200/1/1 (). [VDF]/[I(CF 2 ) 6 I]/[HVI]=50/1/0.1; CF 3 COO) 2 IPh, (□), (CH 3 COO) 2 IPh, (◯), CH3COO) 3 I(-PhCOO—). (⋄).
EXAMPLE 6
[0082] FIG. 5 graphically depicts the dependence of the nature of the PVDF—I chain ends on conversion, and since the total functionality is at least 90%, demonstrates that the polymers made herein are adequate for block copolymer synthesis. [VDF]/[I(CF 2 ) 6 I]/[CF 3 COO) 2 IPh; (CH 3 COO) 2 IPh; CH 3 COO) 3 I(-PhCOO—))=200/1/0.25 (▪), 200/1/0.5 (▴) and 200/1/1 ().
EXAMPLE 7
[0083] Photopolymerizations of VDF at 40° C. were conducted with (CF 3 COO) 2 I-Ph. FIG. 6 sets forth the results of characterization of selected examples of PVDF—I polymers synthesized using hypervalent iodides and various iodine sources.
EXAMPLE 8
[0084] A PVDF homopolymerization can be carried out as described below. In a typical reaction, a 35-mL Ace Glass 8648 #15 Ace-Thread pressure tube equipped with a bushing, and plunger valve with two O-rings and containing a magnetic stir bar, (CF 3 COO) 2 I-Ph, (0.22 g, 0.51 mmol) and solvent (e.g. DMC, 3 mL) was degassed with He and placed in a liquid nitrogen bath. The tube was subsequently opened, and an iodine source (e.g. molecular iodine (I 2 ), 33 mg, 0.13 mmol) was added, followed by the condensation of VDF (1.7 g, 25.8 mmol), directly into the tube, which was then re-degassed with He. The amount of condensed VDF was determined by weighing the closed tube before and after the addition of the monomer. The tube was then placed in behind a plastic shield, in a thermostated oil bath illuminated with a commercial GE Helical 26 W fluorescent white light Hg spiral bulb, from about 2-4 cm. For polymerization kinetics, identical reactions were set up simultaneously and stopped at different polymerization times. At the end of the reaction, the tube was carefully placed in liquid nitrogen, slowly opened behind the shield, and allowed to thaw to room temperature in the hood, with the concomitant release of unreacted VDF. The contents were poured in water, filtered and dried.
EXAMPLE 9
[0085] Enhancing the Leaving Group Ability of Iodine. If C—I bonds can be weakened (analogous to converting an OH group to a tosylate for faster substitution), degenerative transfer may be obtained even with the PVDF—CF 2 —CH 2 —I reverse addition chain ends. Such activation may be accomplished either by their conversion to iodonium species. HVI-like PVDF—I(Ph)OTf iodonium species may also photolyze and promote vinylidene fluoride-controlled radical polymerization (VDF—CRP). Both R F —I(Ph)OTf and R F —CH 2 —I(Ph)OTf initiator models, as well as derivatized PVDF chain ends, may be used in VDF—CRP.
[0086] All patents and patent applications, test procedures, and other documents cited herein are fully incorporated by reference to the extent such disclosure is not inconsistent with this disclosure and for all jurisdictions in which such incorporation is permitted.
[0087] When numerical lower limits and numerical upper limits are listed herein, ranges from any lower limit to any upper limit are contemplated. While the illustrative embodiments of the disclosure have been described with particularity, it will be understood that various other modifications will be apparent to and can be readily made by those skilled in the art without departing from the spirit and scope of the disclosure. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the examples and descriptions set forth herein but rather that the claims be construed as encompassing all the features of patentable novelty which reside in the present disclosure, including all features which would be treated as equivalents thereof by those skilled in the art to which the disclosure pertains.
[0088] The present disclosure has been described above with reference to numerous embodiments and specific examples. Many variations will suggest themselves to those skilled in this art in light of the above detailed description. All such obvious variations are within the full intended scope of the appended claims. | A process is described comprising polymerizing at least one unsaturated monomer (e.g., fluorine substituted alkene monomer) in the presence of a hypervalent iodide radical initiator and a solvent, under reaction conditions and for a time sufficient to polymerize the at least one unsaturated monomer to form a polymer. The present disclosure provides a method for living polymerization of unsaturated monomers (e.g., fluorine substituted alkene monomers), which provides a high level of macromolecular control over the polymerization process and which leads to uniform and controllable polymeric products. The present disclosure also provides a method of functionalization of organic substrates with a CF 3 or perfluoro (R F ) group. | 2 |
[0001] This is a continuation of U.S. application Ser. No. 10/376,447 filed Mar. 3, 2003; which is a division of U.S. application Ser. No. 10/178,838 filed Jun. 25, 2002; which is a continuation of U.S. application Ser. No. 09/849,573 filed May 4, 2001; which is a continuation of U.S. application Ser. No. 09/507,438 filed Feb. 19, 2000 issued as U.S. Pat. No. 6,294,039; which is a division of U.S. application Ser. No. 09/258,999, filed Feb. 26, 1999, issued as U.S. Pat. No. 6,042,677; which is a division of U.S. application Ser. No. 08/896,517, filed Jun. 16, 1997, issued as U.S. Pat. No. 5,910,250; which is a continuation-in-part of U.S. application Ser. No. 08/514,119, filed Aug. 11, 1995, issued as U.S. Pat. No. 5,639,373; and which application Ser. No. 08/896,517 is a continuation-in-part application of U.S. application Ser. No. 08/690,045, filed Jul. 31, 1996, issued as U.S. Pat. No. 5,783,083 which is a continuation-in-part of Ser. No. 08/514,119 and an application claiming the benefit under 35 USC 119(e) of U.S. Provisional Application Ser. No. 60/012,921 filed Mar. 5, 1996; and, application Ser. No. 08/896,517 is a continuation-in-part of U.S. application Ser. No. 08/514,119, filed Aug. 11, 1995, issued as U.S. Pat. No. 5,639,373. PCT/CA96/00536 was filed on Aug. 8, 1996, published as WO97/006880, and claimed priority from U.S. patent Ser. Nos. 08/514,119 and 08/690,045. The disclosure of all the patents and applications listed in this paragraph are hereby incorporated by this reference to them as if they were fully set forth herein.
FIELD OF THE INVENTION
[0002] This invention relates to a membrane filtration apparatus.
BACKGROUND OF THE INVENTION
[0003] The term “vertical skein” in the title (hereafter “skein” for brevity), specifically refers to an integrated combination of structural elements including (i) a multiplicity of vertical fibers of substantially equal length; (ii) a pair of headers in each of which are potted the opposed terminal portions of the fibers so as to leave their ends open; and, (iii) permeate collection means held peripherally in fluid tight engagement with each header so as to collect permeate from the ends of the fibers.
[0004] The term “fibers” is used for brevity, to refer to “hollow fiber membranes” of porous or semipermeable material in the form of a capillary tube or hollow fiber. The term “substrate” refers to a multicomponent liquid feed. A “multicomponent liquid feed” in this art refers, for example, to fruit juices to be clarified or concentrated; wastewater or water containing particulate matter; proteinaceous liquid dairy products such as cheese whey, and the like. The term “particulate matter” is used to refer to micron-sized (from 1 to about 44 μm) and sub-micron sized (from about 0.1 μm to 1 μm) filterable matter which includes not only particulate inorganic matter, but also dead and live biologically active microorganisms, colloidal dispersions, solutions of large organic molecules such as fulvic acid and humic acid, and oil emulsions.
[0005] The term header is used to specify a solid body in which one of the terminal end portions of each one of a multiplicity of fibers in the skein, is sealingly secured to preclude substrate from contaminating the permeate in the lumens of the fibers. Typically, a header is a continuous, generally rectangular parallelpiped of solid resin (thermoplastic or thermosetting) of arbitrary dimensions formed from a natural or synthetic resinous material. In the novel method described hereinbelow, the end portions of individual fibers are potted in spaced-apart relationship in cured resin, most preferably by “potting” the end portions sequentially in at least two steps, using first and second potting materials. The second potting material (referred to as “fixing material”) is solidified or cured after it is deposited upon a “fugitive header” (so termed because it is removable) formed by solidifying the first liquid. Upon removing the fugitive header, what is left is the “finished” or “final” header formed by the second potting material. Of course, less preferably, any prior art method may be used for forming finished headers in which opposed terminal end portions of fibers in a stack of arrays are secured in proximately spaced-apart relationship with each other.
[0006] The '424 patent required potting the opposed ends of a frameless array of fibers and dispensed with the shell of a module; it was an improvement on two preceding configurations disclosed in U.S. Pat. Nos. 5,182,019, and 5,104,535, each of which used frameless arrays and avoided potting the fibers. The efficiency of gas-scrubbing a '424 array was believed to be due, at least in large part, to a substantial portion of the fibers of the fibers in the array lying in transverse relationship to a mass of rising bubbles, referred to herein as a “column of rising bubbles”, so as to intercept the bubbles. Specific examples are illustrated in FIGS. 9, 9A , 10 and 11 of the '424 patent.
[0007] A '424 “array” referred to a bundle of arcuate fibers the geometry of which array was defined by the position of a pair of transversely spaced headers in which the fibers were potted. In the '424 array, as in the array of this invention, each fiber is free to move independently of the others, but the degree of movement in the '424 is unspecified and arbitrary, while in the vertical skein of this invention, movement is critically restricted by the defined length of the fibers between opposed headers. Except for their opposed ends being potted, there is no physical restraint on the fibers of a skein. To avoid confusion with the term “array” as used for the '424 bundle of arcuate fibers, the term “skein fibers” is used herein to refer to plural arrays. An “array” in this invention refers to plural, essentially vertical fibers of substantially equal lengths, the one ends of each of which fibers are closely spaced-apart, either linearly in the transverse (y-axis herein) direction to provide at least one row, and typically plural rows of equidistantly spaced apart fibers. Less preferably, a multiplicity of fibers may be spaced in a random pattern. Typically, plural arrays are potted in a header and enter its face in a generally x-y plane (see FIG. 5 ). The width of a rectangular parallelpiped header is measured along the x-axis, and is the relatively shorter dimension of the rectangular upper surface of the header; and, the header's length, which is its relatively longer dimension, is measured along the y-axis.
[0008] This invention is particularly directed to relatively large systems for the microfiltration of liquids, and capitalizes on the simplicity and effectiveness of a configuration which dispenses with forming a module in which the fibers are confined. As in the '424 patent, the novel configuration efficiently uses a cleansing gas, typically air, discharged near the base of a skein to produce bubbles in a specified size range, and in an amount large enough to scrub the fibers, and to cause the fibers to scrub themselves against one another. Unlike in the '424 system, the fibers in a skein are vertical and do not present an arcuate configuration above a horizontal plane through the horizontal center-line of a header. As a result, the path of the rising bubbles is generally parallel to the fibers and is not crossed by the fibers of a vertical skein. Yet the bubbles scrub the fibers. The restrictedly swayable fibers, because of their defined length, do not get entangled, and do not abrade each other excessively, as is likely in the '424 array. The defined length of the fibers herein minimizes (i) shearing forces where the upper fibers are held in the upper header, (ii) excessive rotation of the upper portion of the fibers, as well as (iii) excessive abrasion between fibers. The fibers of this invention are confined so as to sway in a “zone of confinement” (or “bubble zone”) through which bubbles rise along the outer surfaces of the fibers. The side-to-side displacement of an intermediate portion of each fiber within the bubble zone is restricted by the fiber's length. The bubble zone, in turn, is determined by one or more columns of vertically rising gas bubbles, preferably of air, generated near the base of a skein.
[0009] Since there is no module in the conventional sense, the main physical considerations which affect the operation of a vertical skein in a reservoir of substrate relate to intrinsic considerations, namely, (a) the fiber chosen, (b) the amount of air used, and (c) the substrate to be filtered. Such considerations include the permeability and rejection properties of the fiber, the process flow conditions of substrate such as pressure, rate of flow across the fibers, temperature, etc., the physical and chemical properties of the substrate and its components, the relative directions of flow of the substrate (if it is flowing) and permeate, the thoroughness of contact of the substrate with the outer surfaces of the fibers, and still other parameters, each of which has a direct effect on the efficiency of the skein. The goal is to filter a slow moving or captive substrate in a large container under ambient or elevated pressure, but preferably under essentially ambient pressure, and to maximize the efficiency of a skein which does so (filters) practically and economically.
[0010] In the skein of this invention, all fibers in the plural rows of fibers, staggered or not, rise generally vertically while fixedly held near their opposed terminal portions in a pair of opposed, substantially identical headers to form the skein of substantially parallel, vertical fibers. This skein typically includes a multiplicity of fibers, the opposed ends of which are potted in closely-spaced-apart profusion and bound by potting resin, assuring a fluid-tight circumferential seal around each fiber in the header and presenting a peripheral boundary around the outermost peripheries of the outermost fibers. The position of one fiber relative to another in a skein is not critical, so long as all fibers are substantially codirectional through one face of each header, open ends of the fibers emerge from the opposed other face of each header, and substantially no terminal end portions of fibers are in fiber-to-fiber contact. We found that the skein of fibers, deployed to be restrictedly swayable, were as ruggedly durable as they were reliable in operation.
[0011] The fibers are stated to be “restrictedly swayable”, because the extent to which they may sway is determined by the free length of the fibers relative to the fixedly spaced-apart headers, and the turbulence of the substrate. When a large number of fibers is used in a skein, as is typically the case herein, the movement of a fiber adjacent to others may be modulated by the movement of the others, but the movement of fibers within a skein is constricted. This system is therefore limited to the use of a skein of fibers having a critically defined length relative to the vertical distance between headers of the skein. The defined length limits the side-to-side movement of the fibers in the substrate in which they are deployed, except near the headers where there is negligible movement.
[0012] In the prior art, a vertical skein of fibers in a substrate is typically avoided due to expected problems relating to channelling of the feed. However, because the fibers are restrictedly swayable in a “bubble zone” as described herebelow, the fibers are substantially evenly contacted over their individual surfaces with substrate and provide filtration performance based on a maximized surface which is substantially the sum of the surface areas of all fibers in contact with the substrate. Moreover, because of the ease with which the substrate coats the surfaces of the vertical fibers in a skein, and the accessibility of those surfaces by air bubbles, the fibers may be densely arranged in a header to provide a large membrane surface of up to 1000 m 2 and more.
[0013] One header of a skein is displaceable in any direction relative to the other, either longitudinally (x-axis) or transversely (y-axis), only prior to the headers being vertically fixed in spaced apart parallel relationship within a reservoir, for example, by mounting one header above another, against a vertical wall of the reservoir which functions as a spacer means. This is also true prior to spacing one header above another with other spacer means such as bars, rods, struts, I-beams, channels, and the like, to assemble plural skeins into a “bank of skeins” (“bank” for brevity), in which bank a row of lower headers is directly beneath a row of upper headers. After assembly into a bank, a segment intermediate the potted ends of each individual fiber is displaceable along either the x- or the y-axis, because the fibers are loosely held in the skein. There is essentially no tension on each fiber because the opposed faces of the headers are spaced apart at a distance less than the length of an individual fiber.
[0014] By operating at ambient pressure, mounting the headers of the skein within a reservoir of substrate, and by allowing the fibers restricted movement within the bubble zone in a substrate, we minimize damage to the fibers. Because, a header secures at least 10, preferably from 50 to 50,000 fibers, each generally at least 0.5 m long, in a skein, it provides a high surface area for filtration of the substrate.
[0015] The fibers divide a reservoir into a “feed zone” and a withdrawal zone referred to as a “permeate zone”. The feed of substrate is introduced externally (referred to as “outside-in” flow) of the fibers, and resolved into “permeate” and “concentrate” streams. The skein, or a bank of skeins of this invention is most preferably used for microfiltration with “outside-in” flow. Typically a bank is used in a relatively large reservoir having a volume in excess of 10 L (liters), preferably in excess of 1000 L, such as a flowing stream, more typically a reservoir (pond or tank). Most typically, a bank or plural banks with collection means for the permeate, are mounted in a tank under atmospheric pressure, and permeate is withdrawn from the tank.
[0016] Where a bank or plural banks of skeins are placed within a tank or bioreactor, and no liquid other than the permeate is removed the tank is referred to as a “dead end tank”. Alternatively, a bank or plural banks may be placed within a bioreactor, permeate removed, and sludge disposed of; or, in a tank or clarifier used in conjunction with a bioreactor, permeate removed, and sludge disposed of.
[0017] Operation of the system relies upon positioning at least one skein, preferably a bank, close to a source of sufficient air or gas to maintain a desirable flux, and, to enable permeate to be collected from at least one header. A desirable flux is obtained, and provides the appropriate transmembrane pressure differential of the fibers under operating process conditions. “Transmembrane pressure differential” refers to the pressure difference across a membrane wall, resulting from the process conditions under which the membrane is operating.
[0018] The relationship of flux to permeability and transmembrane pressure differential is set forth by the equation:
J=k ΔP
wherein, J=flux; k=permeability constant;
ΔP=transmembrane pressure differential; and k=1/μm where μ=viscosity of water and, Rm=membrane resistance.
[0021] The transmembrane pressure differential is preferably generated with a conventional non-vacuum pump if the transmembrane pressure differential is sufficiently low in the range from 0.7 kPa (0.1 psi) to 101 kPa (1 bar), provided the pump generates the requisite suction. The term “non-vacuum pump” refers to a pump which generates a net suction side pressure difference, or, net positive suction head (NPSH), adequate to provide the transmembrane pressure differential generated under the operating conditions. By “vacuum pump” we refer to one capable of generating a suction of at least 75 cm of Hg. A pump which generates minimal suction may be used if an adequate “liquid head” is provided between the surface of the substrate and the point at which permeate is withdrawn; or, by using a pump, not a vacuum pump. A non-vacuum pump may be a centrifugal, rotary, crossflow, flow-through, or other type. Moreover, as explained in greater detail below, once the permeate flow is induced by a pump, the pump may not be necessary, the permeate continuing to flow under a “siphoning effect”. Clearly, operating with fibers subjected to a transmembrane pressure differential in the range up to 101 kPa (14.7 psi), a non-vacuum pump will provide adequate service in a reservoir which is not pressurized; and, in the range from 101 kPa to about 345 kPa (50 psi), by superatmospheric pressure generated by a high liquid head, or, by a pressurized reservoir.
[0022] The fibers are not required to be subjected to a narrowly critical transmembrane pressure differential though fibers which operate under a small transmembrane pressure differential are preferred. A fiber which operates under a small transmembrane pressure differential in the range from about 0.7 kPa (0.1 psi) to about 70 kPa (10 psi) may produce permeate under gravity alone, if appropriately positioned relative to the location where the permeate is withdrawn. In the range from 3.5 kPa (0.5 psi) to about 206 kPa (30 psi) a relatively high liquid head may be provided with a pressurized vessel. The longer the fiber, which greater the area and the more the permeate.
[0023] In the specific instance where a bank is used in combination with a source of cleansing gas such as air, both to scrub the fibers and to oxygenate a mixed liquor substrate, most, if not all of the air required, is introduced either continuously or intermittently, near the base of the fibers near the lower header. The perforations through which the gas is discharged near the header are located close enough to the fibers so as to provide columns of relatively large bubbles, preferably larger than about 1 mm in nominal diameter, which codirectionally contact the fibers and flow vertically along their outer surfaces scrubbing them. The outer periphery of the columns of bubbles define the zone of confinement in which the scrubbing force exerted by the bubbles on the fibers, keeps their surfaces sufficiently free of attached microorganisms and deposits of inanimate particles to provide a relatively high and stable flow of permeate over many weeks, if not months of operation. The significance of this improvement will be better appreciated when it is realized that the surfaces of fibers in conventional modules are cleaned nearly every day, and sometimes more often.
[0024] Because this system, like the '424 system, does away with using a shell, there is no void space within a shell to be packed with fibers; and, because of gas being introduced proximately to, and near the base of skein fibers, there is no need to maintain a high substrate velocity across the surface of the fibers to keep the surfaces of the fibers clean. As a result, there is virtually no limit to the number of restrictedly swayable fibers which may be used in a skein, the practical limit being set by (i) the ability to pot the ends of the fibers reliably; (ii) the ability to provide sufficient air to the surfaces of essentially all the fibers, and (iii) the number of banks which may be deployed in a tank, pond or lake, the number to be determined by the size of the body of water, the rate at which permeate is to be withdrawn, and, the cost of doing so.
[0025] Typically, a relatively large number of long fibers, at least 100, is used in a skein of restrictedly swayable fibers, the fibers operate under a relatively low transmembrane pressure differential, and permeate is withdrawn with a non-vacuum pump. If the liquid head, measured as the vertical distance between the level of substrate and the level from which permeate is to be withdrawn, is greater than the transmembrane pressure differential under which the fiber operates, the permeate will be separated from the remaining substrate, due to gravity.
[0026] Irrespective of whether a non-vacuum pump, vacuum pump, or other type of pump is used, or permeate is withdrawn with a siphoning effect, it is essential that the fibers in a skein be positioned in a generally vertical attitude, rising above the lower header. An understanding of how a vertical skein operates will make it apparent that, since fibers in a skein are anchored at the base of the skein by the lower header, the specific gravity of the fibers relative to that of the substrate is immaterial and will not affect their vertical disposition.
[0027] The unique method of forming a header disclosed herein allows one to position a large number of fibers, in closely-spaced apart relationship, randomly relative to one another, or, in a chosen geometric pattern, within each header of synthetic resinous material. It is preferred to position the fibers in arrays before they are potted to ensure that the fibers are spaced apart from each other precisely, and, to avoid wasting space on the face of a header; it is essential, for greatest reliability, that the fibers not be contiguous. By sequentially potting the terminal portions of fibers in stages as described herein, the fibers may be cut to length in an array, either after, or prior to being potted. The use of a razor-sharp knife, or scissors, or other cutting means to do so, does not decrease the open cross-sectional area of the fibers' bores (“lumens”). The solid resin forms a circumferential seal around the exterior terminal portions of each of the fibers, open ends of which protrude through the permeate-discharging face of each header, referred to as the “aft” face.
[0028] Further, one does not have to cope with the geometry of a frame, the specific function of which is to hold fibers in a particular arrangement within the frame. In a skein, the sole function of the header spacing means is to maintain a fixed vertical distance between headers which are not otherwise spaced apart. In a skein of this invention, there is no frame.
[0029] The skein of this invention is most preferably used to treat wastewater in combination with a source of an oxygen-containing gas which is bubbled within the substrate, near the base of a lower header, either within a skein or between adjacent skeins in a bank, for the specific purpose of scrubbing the fibers and oxygenating the mixed liquor in activated sludge, such as is generated in the bioremediation of wastewater. It was found that, as long as enough air is introduced near the base of each lower header to keep the fibers awash in bubbles, and the fibers are restrictedly swayable in the activated sludge, a build-up of growth of microbes on the surfaces of the fibers is inhibited while permeate is directly withdrawn from activated sludge, and excellent flow of permeate is maintained over a long period. Because essentially all surface portions of the fibers are contacted by successive bubbles as they rise, whether the air is supplied continuously or intermittently, the fibers are said to be “awash in bubbles.”
[0030] The use of an array of fibers in the direct treatment of activated sludge in a bioreactor, is described in an article titled “Direct Solid-Liquid Separation Using Hollow Fiber Membrane in an Activated Sludge Aeration Tank” by Kazuo Yamamoto et al in Wat. Sci. Tech . Vol. 21, Brighton pp 43-54, 1989, and discussed in the '424 patent, the disclosure of which is incorporated by reference thereto as if fully set forth herein. The relatively poor performance obtained by Yamamoto et al was mainly due to the fact that they did not realize the critical importance of maintaining flux by aerating a skein of fibers from within and beneath the skein. They did not realize the necessity of thoroughly scrubbing substantially the entire surfaces of the fibers by flowing bubbles through the skein to keep the fibers awash in bubbles. This requirement becomes more pronounced as the number of fibers in the skein increases.
[0031] As will presently be evident, since most substrates are contaminated with micron and submicron size particulate material, both organic and inorganic, the surfaces of the fibers in any practical membrane device must be maintained in a clean condition to obtain a desirable specific flux. To do this, the most preferred use of the skein as a membrane device is in a bank in combination with a gas-distribution means, which is typically used to distribute air, or oxygen-enriched air between the fibers, from within the skein, or between adjacent skeins, at the bases thereof.
[0032] Tests using the device of Yamamoto et al indicate that when the air is provided outside the skein the flux decreases much faster over a period of as little as 50 hr, confirming the results obtained by them. This is evident in FIG. 1 described in greater detail below, in which the graphs show results obtained by Yamamoto et al, and the '424 array, as well as those with the vertical skein, all three assemblies using essentially identical fibers, under essentially identical conditions.
[0033] The investigation of Yamamoto et al with downwardly suspended fibers was continued and recent developments were reported in an article titled “Organic Stabilization and Nitrogen Removal in Membrane Separation Bio-reactor for Domestic Wastewater Treatment” by C. Chiemchaisri et al delivered in a talk to the Conference on Membrane Technology in Wastewater Management, in Cape Town, South Africa, Mar. 2-5, 1992, also discussed in the '424 patent. The fibers were suspended downwardly and highly turbulent flow of water in alternate directions, was essential.
[0034] It is evident that the disclosure in either the Yamamoto et al or the Chiemchaisri et al reference indicated that the flow of air across the surfaces of the suspended fibers did little or nothing to inhibit the attachment of microorganisms from the substrate.
SUMMARY OF THE INVENTION
[0035] It has been discovered that bubbles of a fiber-cleansing gas (“scrubbing gas”) flowing parallel to fibers in a vertical skein are more effective than bubbles which are intercepted by arcuate fibers crossing the path of the rising bubbles. Bubbles of an oxygen-containing gas to promote growth of microbes unexpectedly fails to build-up growth of microbes on the surfaces of the fibers because the surfaces are “vertically air-scrubbed”. Deposits of animate and/or inanimate particles upon the surfaces of fibers are minimized when the restrictedly swayable fibers are kept awash in codirectionally rising bubbles which rise with sufficient velocity to exert a physical scrubbing force (momentum provides the energy) to keep the fibers substantially free of deleterious deposits. Thus, an unexpectedly high flux is maintained over a long period during which permeate is produced by outside-in flow through the fibers.
[0036] It has also been discovered that permeate may be efficiently withdrawn from a substrate for a surprisingly long period, in a single stage, essentially continuous filtration process, by mounting a pair of headers in vertically spaced apart relationship, one above another, within the substrate which directly contacts a multiplicity of long vertical fibers in a “gas-scrubbed assembly” comprising a skein and a gas-distribution means. The skein has a surface area which is at least >1 m 2 , and opposed spaced-apart ends of the fibers are secured in spaced-apart headers, so that the fibers, when deployed in the substrate, acquire a generally vertical profile therewithin and sway within the bubble zone defined by at least one column of bubbles. The length of fibers between opposed surfaces of headers from which they extend, is in a critical range from at least 0.1% (percent) longer than the distance separating those opposed faces, but less than 5% longer. Usually the length of fibers is less than 2% longer, and most typically, less than 1% longer, so that sway of the fibers is confined within a vertical zone of movement, the periphery of which zone is defined by side-to-side movement of outer fibers in the skein; and, the majority of the fibers near the periphery move in a slightly larger zone than one defined by the projected area of one header upon the other. Though the distance between headers is fixed during operation, the distance is preferably adjustable to provide an optimum length of fibers, within the aforesaid ranges, between the headers. It has been found that for no known reason, fibers which are more than 5% but less than 10% longer than the fixed distance between the opposed faces of the headers of a skein, tend to shear off at the face; and those 10% longer tend to clump up in the bubble zone.
[0037] The terminal end portions of the fibers are secured non-contiguously in each header, that is, the surface of each fiber is sealingly separated from that of another adjacent fiber with cured potting resin. Preferably, for maximum utilization of space on a header, the fibers are deliberately set in a geometrically regular pattern. Typically permeate is withdrawn from the open ends of fibers which protrude from the permeate-discharging aft (upper) face of a header. The overall geometry of potted fibers is determined by a ‘fiber-setting form’ used to set individual fibers in an array. The skein operates in a substrate held in a reservoir at a pressure in the range from 1 atm to an elevated pressure up to about 10 atm in a pressurized vessel, without being confined within the shell of a module.
[0038] It is therefore a general object of this invention to provide a novel, economical and surprisingly trouble-free membrane device, for providing an alternative to both, a conventional module having plural individual arrays therewithin, and also to a frameless array of arcuate fibers; the novel device includes, (i) a vertical skein of a multiplicity of restrictedly swayable fibers, together having a surface area in the range from 1 m 2 to 1000 m 2 , preferably from 10 m 2 to 100 m 2 , secured only in spaced-apart headers; and (ii) a gas-scrubbing means which produces at least one column of bubbles engulfing the skein. A skein includes permeate pans disposed, preferably non-removably, within a substrate held in a reservoir of arbitrary proportions, the reservoir typically having a volume in excess of 100 L (liters), generally in excess of 1000 L. A fluid component is to be selectively removed from the substrate.
[0039] It is a specific object of this invention to provide a membrane device having hollow fibers for removing permeate from a substrate, comprising, a skein of a multiplicity of fibers restrictedly swayable in the substrate, the opposed terminal end portions of which fibers in spaced-apart relationship, are potted in a pair of headers, one upper and one lower, each adapted to be mounted in vertically spaced apart generally parallel relationship, one above the other, within the substrate; essentially all the ends of fibers in both headers are open so as to pass permeate through the headers; the fibers in a skein have a length in the range from at least 0.1% greater, but less than 5% greater than the direct distance between opposed faces of the upper and lower headers, so as to present the fibers, when they are deployed, in an essentially vertical configuration; permeate is collected in a collection means, such as a permeate pan; and, permeate is withdrawn through a ducting means including one or more conduits and appropriate valves. Permeate may be withdrawn from only one, usually the upper permeate collection means (pan or end-cap), or, in skeins of large surface area greater than 200 m 2 , from both (upper and lower) pans or end-caps. Most preferably, air is introduced between skein fibers by an air-tube potted centrally axially within the upper end-cap, the air-tube supplying air to a sparger near the base of the skein fibers, and simultaneously providing a spacer means to position and space the lower end-cap the requisite distance from the upper end-cap. The sparger is part of a gas-supply means which supplies cleansing gas. The air-tube may be internally provided with a concentric permeate withdrawal tube axially extending to the permeate collection zone in the lower end-cap, and in open fluid communication with it, to withdraw permeate from both the upper and lower end-caps.
[0040] It has also been discovered that skein fibers are maintained sufficiently free from particulate deposits with surprisingly little cleansing gas, so that the specific flux at equilibrium is maintained over a long period, typically from 50 hr to 1500 hr, because the skein is immersed so as to present a generally vertical profile, and, the skein is maintained awash in bubbles either continuously or intermittently generated by a gas-distribution means (“air-manifold”). The air-manifold is disposed adjacent the skein's lower header to generate a column of rising bubbles within which column the fibers are awash in bubbles. A bank of skeins is “gas-scrubbed” with plural air-tubes disposed between the lower headers of adjacent skeins, most preferably, also adjacent the outermost array of the first and last skeins, so that for “n” headers there are “n+1” air-manifolds. Each header is preferably in the shape of a rectangular parallelpiped, the upper and lower headers having the same transverse (y-axis) dimension, so that plural headers are longitudinally stackable (along the x-axis). Common longitudinally positioned linear air-tubes, or, individual, longitudinally spaced apart vertically rising air-tubes, service the bank, and one or more permeate tubes withdraw permeate.
[0041] It is therefore a general object of this invention to provide a gas-scrubbed assembly of fibers for liquid filtration, the assembly comprising, (a) bank of gas-scrubbed skeins of fibers which separate a desired permeate from a large body of multicomponent substrate having finely divided particulate matter in the range from 0.1 μm-44 μm dispersed therein, (b) each skein comprising at least 20 fibers having upper and lower terminal portions potted spaced-apart, in upper and lower headers, respectively, the fibers being restrictedly swayable in a bubble zone, and (c) a shaped gas-distribution means adapted to provide a profusion of vertically ascending bubbles near the lower header, the length of the fibers being from at least 0.1% but less than 5% greater than the distance between the opposed faces of the headers. The gas-distribution means has through-passages therein through which gas is flowed at a flow rate which is proportional to the number of fibers. The flow rate is generally in the range from 0.47-14 cm 3 /sec per fiber (0.001-0.03 scfm/fiber) (standard ft 3 per minute per fiber), typically in the range from 1.4-4.2 cm 3 /sec/fiber (0.003-0.009 scfm/fiber). The surface area of the fibers is not used to define the amount of air used because the air travels substantially vertically along the length of each fiber. The gas generates bubbles having an average diameter in the range from about 0.1 mm to about 25 mm, or even larger.
[0042] It is a specific object of this invention to provide the aforesaid novel gas-scrubbed assembly comprising, a bank of vertical skeins and a shaped gas-distribution means for use with the bank, in a substrate in which microorganisms grow, the assembly being used in combination with vertically adjustable spacer means for mounting the headers in vertically spaced apart relationship, and in open fluid communication with collection means for collecting the permeate; means for withdrawing the permeate; and, sufficient air is flowed through the shaped gas-distribution means to generate enough bubbles flowing upwardly through the skein, between and parallel to the fibers so as to keep the surfaces of the fibers substantially free from deposits of live microorganisms as well as small inanimate particles which may be present in the substrate.
[0043] It has still further been discovered that a system utilizing a bank of vertical skeins of fibers potted in headers vertically spaced-apart by spacer means, and deployed in a substrate containing particulate material, in combination with a proximately disposed gas-distribution means to minimize fouling of the membranes, may be operated to withdraw permeate under gravity alone, so that the cost of any pump to withdraw permeate is avoided, provided the net positive suction head corresponding to the vertical height between the level of substrate, and the location of withdrawal of permeate, provides the transmembrane pressure differential under which the fibers function in the skein.
[0044] It is therefore a general object of this invention to provide the foregoing system in which opposed terminal end portions of skein fibers are essentially free from fiber-to-fiber contact after being potted in upper and lower headers kept vertically spaced-apart with spacer means, the skein being unconfined in a shell of a module and deployed in the substrate without the fibers being supported during operation except by the spacer means which support only the headers; the headers being mounted so that the fibers present a generally vertical profile yet are restrictedly swayable in a zone of confinement defined by rising bubbles; means for mounting each header in open fluid communication with collection means for collecting permeate, and, means for withdrawing the permeate; and, shaped gas-distribution means adapted to generate bubbles from micron-size to 25 mm in nominal diameter, most preferably in the size range from 1 mm to 20 mm, the bubbles flowing upwardly through and parallel to the fibers at a flow rate chosen from the range specified hereabove; whereby the fibers are scrubbed with bubbles and resist the attachment of growing microorganisms and any other particulate matter to the surfaces of the fibers, so as to maintain a desirable specific flux during operation.
[0045] Still further, a low cost process has been discovered for treating a multicomponent substrate under pressure ranging from 1-10 atm in a pressurizable vessel, particularly for example, an aqueous stream containing finely divided inorganic matter such as silica, silicic acid, or, activated sludge, when the substrate is confined in a large tank or pond, by using a bank of vertical skeins each comprising restrictedly swayable unsupported fibers potted in headers in open fluid communication with a means for withdrawing permeate, in combination with a source of air which generates bubbles near the lower header.
[0046] It is therefore a general object of this invention to provide a process for maintaining relatively clean fiber surfaces in an array of a membrane device while separating a permeate from a substrate, the process comprising,
submerging a skein of restrictedly swayable substantially vertical fibers within the substrate so that upper and lower headers of the skein are mounted one above the other with a multiplicity of fibers secured between said headers, the fibers having their opposed terminal portions in open fluid communication with permeate collecting means in fluid-tight connection with said headers; the fibers operating under a transmembrane pressure differential in the range from about 0.7 kPa (0.1 psi) to about 345 kPa (50 psi), and a length from at least 0.1% to about 2% greater than the direct distance between the opposed faces of upper and lower headers, so as to present, when the fibers are deployed, a generally vertical skein of fibers; maintaining an essentially constant flux substantially the same as the equilibrium flux initially obtained, indicating that the surfaces of the fibers are substantially free from further build-up of deposits once the equilibrium flux is attained; collecting the permeate; and, withdrawing the permeate.
[0051] It has still further been discovered that the foregoing process may be used in the operation of an anaerobic or aerobic biological reactor which has been retrofitted with the membrane device of this invention. The anaerobic reactor is a closed vessel and the scrubbing gas is a molecular oxygen-free gas, such as nitrogen.
[0052] It is therefore a general object of this invention to provide an aerobic biological reactor retrofitted with at least one gas-scrubbed bank of vertical skeins, each skein made with from 500 to 5000 fibers in the range from 1 m to 3 m long, in combination with a permeate collection means, and to provide a process for the reactor's operation without being encumbered by the numerous restrictions and limitations imposed by a secondary clarification system.
[0053] A novel composite header is provided for a bundle of hollow fiber membranes or “fibers”, the composite header comprising a molded, laminated body of arbitrary shape, having an upper lamina formed from a “fixing” (potting) material which is laminated to a lower lamina formed from a “fugitive” potting material. The terminal portions of the fibers are potted in the fugitive potting material when it is liquid, preferably forming a generally rectangular parallel-piped in which the open ends of the fibers (until potted) are embedded and plugged, keeping the fibers in closely spaced-apart substantially parallel relationship. The plugged ends of the fibers fail to protrude through the lower (aft) face of the lower lamina, while the remaining lengths of the fibers extend through the upper face of the lower lamina. The upper lamina extends for a height along the length of the fibers sufficient to maintain the fibers in the same spaced-apart relationship relative to one and another as their spaced-apart relationship in the lower portion. If desired, the composite header may include additional laminae, for example, a “cushioning” lamina overlying the fixing lamina, to cushion each fiber around its embedded outer circumference; and, a “gasketing” lamina to provide a suitable gasketing material against which the permeate collection means may be mounted.
BRIEF DESCRIPTION OF THE DRAWINGS
[0054] The foregoing and additional objects and advantages of the invention will best be understood by reference to the following detailed description, accompanied by schematic illustrations of preferred embodiments of the invention, in which illustrations like reference numerals refer to like elements, and in which:
[0055] FIG. 1 is a graph in which the variation of flux is plotted as a function of time, showing three curves for three runs made with three different arrays, in each case, using the same amount of air, the identical membranes and the same membrane surface area. The results obtained by Yamamoto et al are plotted as curve 2 (under conditions modified to give them the benefit of doubt as to the experimental procedure employed, as explained below); the flux obtained using the gas-scrubbed assembly of the '424 patent is shown as curve 1 ; and the flux obtained using the gas-scrubbed assembly of this invention is shown as curve 3 .
[0056] FIG. 2 is a perspective exploded view schematically illustrating a membrane device comprising a skein of fibers, unsupported during operation of the device, with the ends of the fibers potted in a lower header, along with a permeate collection pan, and a permeate withdrawal conduit. By “unsupported” is meant ‘not supported except for spacer means to space the headers’.
[0057] FIG. 2A is an enlarged detail side elevational view of a side wall of a collection pan showing the profile of a header-retaining step atop the periphery of the pan.
[0058] FIG. 2B is a bottom plan view of the header showing a random pattern of open ends protruding from the aft face of a header when fibers are potted after they are stacked in rows and glued together before being potted.
[0059] FIG. 3 is a perspective view of a single array, schematically illustrated, of a row of substantially coplanarly disposed parallel fibers secured near their opposed terminal ends between spaced apart cards. Typically, multiple arrays are assembled before being sequentially potted.
[0060] FIG. 4 illustrates a side elevational view of a stack of arrays near one end where it is together, showing that the individual fibers (only the last fiber of each linear array is visible, the remaining fibers in the array being directly behind the last fiber) of each array are separated by the thickness of a strip with adhesive on it, as the stack is held vertically in potting liquid.
[0061] FIG. 5 is a perspective view schematically illustrating a skein with its integral finished header, its permeate collection pan, and twin air-tubes feeding an integral air distribution manifold potted in the header along an outer edge of the skein fibers.
[0062] FIG. 6 is a side elevational view of an integral finished header showing details of a permeate pan submerged in substrate, the walls of the header resting on the bottom of a reservoir, and multiple air-tubes feeding integral air distribution manifolds potted in the header along each outer edge of the skein fibers.
[0063] FIG. 7A is a perspective view schematically illustrating an air-manifold from which vertical air-tubes rise.
[0064] FIG. 7B is a perspective view schematically illustrating a tubular air-manifold having a transverse perforated portion, positioned by opposed terminal portions.
[0065] FIG. 8 is a perspective view of an integral finished header having plural skeins potted in a common header molded in an integral permeate collection means with air-tubes rising vertically through the header between adjacent skeins, and along the outer peripheries of the outer skeins.
[0066] FIG. 9 is a detail, not to scale, illustratively showing a gas distribution means discharging gas between arrays in a header, and optionally along the sides of the lower header.
[0067] FIG. 10 is a perspective view schematically illustrating a pair of skeins in a bank in which the upper headers are mounted by their ends on the vertical wall of a tank. The skeins in combination with a gas-distribution means form a “gas-scrubbing assembly” deployed within a substrate, with the fibers suspended essentially vertically in the substrate. Positioning the gas-distribution means between the lower headers (and optionally, on the outside of skein fibers) generate masses (or “columns”) of bubbles which rise vertically, codirectionally with the fibers, yet the bubbles scrub the outer surfaces of the fibers.
[0068] FIG. 11 is a perspective view of another embodiment of the scrubbing-assembly showing plural skeins (only a pair is shown) connected in a bank with gas-distribution means disposed between successive skeins, and, optionally, with additional gas-distribution means fore and aft the first and last skeins, respectively.
[0069] FIG. 12 is an elevational view schematically illustrating a bank of skeins mounted against the wall of a bioreactor, showing the convenience of having all piping connections outside the liquid.
[0070] FIG. 13 is a plan view of the bioreactor shown in FIG. 12 showing how multiple banks of skeins may be positioned around the circumference of the bioreactor to form a large permeate extraction zone while a clarification zone is formed in the central portion with the help of baffles.
[0071] FIG. 14 illustratively shows another embodiment of the skein in which the permeate tube is concentrically disposed within the air supply tube and both are potted, near their lower ends in the lower header. Ports in the lower end of the air supply tube provide air near the base of the skein fibres.
[0072] FIGS. 14-17 specifically illustrate preferred embodiments of the cylindrical vertical skein.
[0073] FIG. 18 is a bar graph which shows the average flux over 24 hours period fro each orientation of the skein.
[0074] FIGS. 19-20 are a plots of flux as function of time, until the flow reaches an equilibrium value.
DETAILED DESCRIPTION OF THE INVENTION
[0075] The skein of this invention may be used in a liquid—liquid separation process of choice, and more generally, in various separation processes. The skein is specifically adapted for use in microfiltration processes used to remove large organic molecules, emulsified organic liquids and colloidal or suspended solids, usually from water. Typical applications are (i) in a membrane bioreactor, to produce permeate as purified water and recycle biomass; for (ii) tertiary filtration of wastewater to remove suspended solids and pathogenic bacteria; (iii) clarification of aqueous streams including filtration of surface water to produce drinking water (removal of colloids, long chain carboxyic acids and pathogens); (iv) separation of a permeable liquid component in biotechnology broths; (v) dewatering watering of metal hydroxide sludges; and, (vi) filtration of oily wastewater, inter alia.
[0076] The problem with using a conventional membrane module to selectively separate one fluid from another, particularly using the module in combination with a bioreactor, and the attendant costs of operating such a system, have been avoided. In those instances where an under-developed country or distressed community lacks the resources to provide membrane modules, the most preferred embodiment of this invention is adapted for use without any pumps. In those instances where a pump is conveniently used, a vacuum pump is unnecessary, adequate driving force being provided by a simple centrifugal pump incapable of inducing a vacuum of 75 cm Hg on the suction side.
[0077] The fibers used to form the skein may be formed of any conventional membrane material provided the fibers are flexible and have an average pore cross sectional diameter for microfilitration, namely in the range from about 1000 Å to 10000 Å. Preferred fibers operate with a transmembrane pressure differential in the range from 7 kPa (1 psi)-69 kPa (10 psi) and are used under ambient pressure with the permeate withdrawn under gravity. The fibers are chosen with a view to perform their desired function, and the dimensions of the skein are determined by the geometry of the headers and length of the fibers. It is unnecessary to confine a skein in a modular shell, and a skein is not.
[0078] Preferred fibers are made of organic polymers and ceramics, whether isotropic, or anisotropic, with a thin layer or “skin” on the outside surface of the fibers. Some fibers may be made from braided cotton covered with a porous natural rubber latex or a water-insoluble cellulosic polymeric material. Preferred organic polymers for fibers are polysulfones, poly(styrenes), including styrene-containing copolymers such as acrylonitrile-styrene, butadiene-styrene and styrene-vinylbenzylhalide copolymers, polycarbonates, cellulosic polymers, polypropylene, poly(vinyl chloride), poly(ethylene terephthalate), and the like disclosed in U.S. Pat. No. 4,230,463 the disclosure of which is incorporated by reference thereto as if fully set forth herein. Preferred ceramic fibers are made from alumina, by E. I. duPont deNemours Co. and disclosed in U.S. Pat. No. 4,069,157.
[0079] Typically, there is no cross flow of substrate across the surface of the fibers in a “dead end” tank. If there is any flow of substrate through the skein in a dead end tank, the flow is due to aeration provided beneath the skein, or to such mechanical mixing as may be employed to maintain the solids in suspension. There is more flow through the skein in a tank into which substrate is being continuously flowed, but the velocity of fluid across the fibers is generally too insignificant to deter growing microorganisms from attaching themselves, or suspended particles, e.g. microscopic siliceous particles, from being deposited on the surfaces of the fibers.
[0080] For hollow fiber membranes, the outside diameter of a fiber is at least 20 μm and may be as large as about 3 mm, typically being in the range from about 0.1 mm to 2 mm. The larger the outside diameter the less desirable the ratio of surface area per unit volume of fiber. The wall thickness of a fiber is at least 5 μm and may be as much as 1.2 mm, typically being in the range from about 15% to about 60% of the outside diameter of the fiber, most preferably from 05 mm to 1.2 mm.
[0081] As in a '424 array, but unlike in a conventional module, the length of a fiber in a skein is essentially independent of the strength of the fiber, or its diameter, because the skein is buoyed both by bubbles and the substrate in which it is deployed. The length of fibers in the skein is preferably determined by the conditions under which the skein is to operate. Typically fibers range from 1 m to about 5 m long, depending upon the dimensions of the body of substrate (depth and width) in which the skein is deployed.
[0082] The fixing material to fix the fibers in a finished header is most preferably either a thermosetting or thermoplastic synthetic resinous material, optionally reinforced with glass fibers, boron or graphite fibers and the like. Thermoplastic materials may be crystalline, such as polyolefins, polyamides (nylon), polycarbonates and the like, semi-crystalline such as polyetherether ketone (PEEK), or substantially amorphous, such as poly(vinyl chloride) (PVC), polyurethane and the like. Thermosetting resins commonly include polyesters, polyacetals, polyethers, cast acrylates, thermosetting polyurethanes and epoxy resins. Most preferred as a “fixing” material (so termed because it fixes the locations of the fibers relative to each other) is one which when cured is substantially rigid in a thickness of about 2 cm, and referred to generically as a “plastic” because of its hardness. Such a plastic has a hardness in the range from about Shore D 50 to Rockwell R 110 and is selected from the group consisting of epoxy resins, phenolics, acrylics, polycarbonate, nylon, polystyrene, polypropylene and ultra-high molecular weight polyethylene (UHMW PE). Polyurethane such as is commercially available under the brand names Adiprenee® from Uniroyal Chemical Company and Airthane® from Air Products, and commercially available epoxy resins such as Epon 828 are excellent fixing materials.
[0083] The number of fibers in an array is arbitrary, typically being in the range from about 1000 to about 10000 for commercial applications, and the preferred surface area for a skein is in the range from 10 m 2 to 100 m 2 .
[0084] The particular method of securing the fibers in each of the headers is not narrowly critical, the choice depending upon the materials of the header and the fiber, and the cost of using a method other than potting. However, it is essential that each of the fibers be secured in fluid-tight relationship within each header to avoid contamination of permeate. This is effected by potting the fibers essentially vertically, in closely-spaced relationship, either linearly in plural equally spaced apart rows across the face of a header in the x-y plane; or alternatively, randomly, in non-linear plural rows. In the latter, the fibers are displaced relative to one another in the lateral direction.
[0085] FIG. 1 presents the results of a comparison of three runs made, one using the teachings of Yamamoto in his'89 publication (curve 2 ), but using an aerator which introduced air from the side and directed it radially inwards, as is shown in Chiemchaisri et al. A second run (curve 1 ) uses the gas-scrubbed assembly of the '424 patent, and the third run (curve 3 ) uses the gas-scrubbed skein of this invention. The specific flux obtained with an assembly of an inverted parabolic array with an air distributor means (Yamamoto et al), as disclosed in Wat. Sci. Tech. Vol. 21, Brighton pp 43-54, 1989, and, the parabolic array by Cote et al in the '424 patent, are compared to the specific flux obtained with the vertical skein of this invention.
[0086] The comparison is for the three assemblies having fibers with nominal pore size 0.2 μm with essentially identical bores and surface area in 80 L tanks filled with the same activated sludge substrate. The differences between the stated experiment of Yamamoto et al, and that of the '424 patent are of record in the '424 patent, and the conditions of the comparison are incorporated by reference thereto as if fully set forth herein. The vertical skein used herein differs from the '424 skein only in the vertical configuration of the 280 fibers each of which was about 1% longer than the distance between the spaced apart headers during operation. The flow rate of air for the vertical skein is 1.4 m 3 /hr/m 2 using a coarse bubble diffuser.
[0087] It will be evident from FIG. 1 in which the specific flux, liters/meter 2 hr/kPa (conventionally written as (1 mh/kPa), is plotted as a function of operating time for the three assemblies, that the curve, identified as reference numeral 3 for the flux for the vertical skein, provides about the same specific flux as the parabolic skein, identified as reference numeral 1 . As can be seen, each specific flux reaches an equilibrium condition within less than 50 hr, but after about 250 hr, it is seen that the specific flux for the inverted parabolic array keeps declining but the other two assemblies reach an equilibrium.
[0088] Referring to FIG. 2 there is illustrated, in exploded view a portion of a membrane device referred to as a “vertical skein” 10 , comprising a lower header 11 of a pair of headers, the other upper header (not shown) being substantially identical; a collection pan 20 to collect the permeate; and, a permeate withdrawal conduit 30 . The header shown is a rectangular prism since this is the most convenient shape to make, if one is going to pot fibers 12 in a potting resin such as a polyurethane or an epoxy. Though the fibers 12 are not shown as close together as they would normally be, it is essential that the fibers are not in contact with each other but that they be spaced apart by the cured resin between them.
[0089] As illustrated, the open ends of the terminal portion 12 ′ of the fibers are in the same plane as the lower face of the header 11 because the fibers are conventionally potted and the header sectioned to expose the open ends. A specific potting procedure in which the trough of a U-shaped bundle of fibers is potted, results in forming two headers. This procedure is described in the '424 patent (col 17, lines 44-61); however, even cutting the potted fibers with a thin, high-speed diamond blade, tends to damage the fibers and initiate the collapse of the circumferential wall. In another conventional method of potting fibers, described in U.S. Pat. No. 5,202,023, bundled fibers have their ends dipped in resin or paint to prevent potting resin penetration into the bores of the fibers during the potting process. The ends of the bundle are then placed in molds and uncured resin added to saturate the ends of the fiber bundle and fill the spaces between the individual fibers in the bundle and the flexible tubing in which the bundle is held. The cured molded ends are removed from the molds and the molded ends cut off (see, bridging cols 11 and 12 ). In each art method, sectioning the mold damages the embedded fibers.
[0090] Therefore a novel method is used to form a header 11 in the form of a rectangular prism. The method requires forming a composite header with two liquids. A first liquid fugitive material, when solidified (cured), forms a “fugitive lamina” of the composite header; a second liquid of non-fugitive fixing material forms a “fixing lamina”. By a “fugitive material” we refer to a material which is either (i) soluble in a medium in which the fibers and fixing material are not soluble, or (ii) fluidizable by virtue of having a melting point (if the material is crystalline) below that which might damage the fibers or fixing material; or, the material has a glass transition temperature Tg (if the material is non-crystalline), below that which might damage the fibers or material(s) forming the non-fugitive header; or (iii) both soluble and fluidizable.
[0091] The first liquid is poured around terminal portions of fibers, allowed to cool and solidify into a fugitive lamina; the fibers in the fugitive lamina are then again potted, this time by pouring the second liquid over the solid fugitive lamina.
[0092] In greater detail, the method for forming a finished header for skein fibers comprises,
forming a stack of at least two superimposed essentially coplanar and similar arrays, each array comprising a chosen number of fibers supported on a support means having a thickness corresponding to a desired lateral spacing between adjacent arrays; holding the stack in a first liquid with terminal portions of the fibers submerged, until the liquid solidifies into a first shaped lamina, provided that the first liquid is unreactive with material of the fibers; pouring a second liquid over the first shaped lamina to embed the fibers to a desired depth, and solidifying the second liquid to form a fixing lamina upon the first shaped lamina, the second liquid also being substantially unreactive with either the material of the fibers or that of the first shaped lamina; whereby a composite header is formed in which terminal portions of the fibers are potted, preferably in a geometrically regular pattern, the composite header comprising a laminate of a fugitive lamina of fugitive material and a contiguous finished header of fixing lamina; and thereafter, removing the first shaped lamina without removing a portion of the fixing lamina so as to leave the ends of the fibers open and protruding from the aft face of the header, the open ends having circular cross-section.
[0097] The step-wise procedure for forming an array “A” with the novel header is described with respect to an array illustrated in FIG. 3 , as follows:
[0098] A desired number of fibers 12 are each cut to about the same length with a sharp blade so as to leave both opposed ends of each fiber with an essentially circular cross-section. The fibers are coplanarly disposed side-by-side in a linear array on a planar support means such as strips or cards 15 and 16 . Preferably the strips are coated with an adhesive, e.g. a commercially available polyethylene hot-melt adhesive, so that the fibers are glued to the strips and opposed terminal portions 12 ″ respectively of the fibers, extend beyond the strips. Intermediate portions 12 ′ of the fibers are thus secured on the strips. Alternatively, the strips may be grooved with parallel spaced-apart grooves which snugly accommodate the fibers. The strips may be flexible or rigid. If flexible, strips with fibers adhered thereto, are in turn, also adhered to each other successively so as to form a progressively stiffer stack for a header having a desired geometry of potted fibers. To avoid gluing the strips, a regular pattern of linear rows may be obtained by securing multiple arrays on rigid strips in a stack, with rubber bands 18 or other clamping means. The terminal portions 12 ″ are thus held in spaced-apart relationship, with the center to center distance of adjacent fibers preferably in the range from 1.2 (1.2 d) to about 5 times (5 d) the outside diameter ‘d’ of a fiber. Spacing the fibers further apart wastes space and spacing them closer increases the risk of fiber-to-fiber contact near the terminal end portions when the ends are potted. Preferred center-to-center spacing is from about 1.5 d to 2 d. The thickness of a strip and/or adhesive is sufficient to ensure that the fibers are kept spaced apart. Preferably, the thickness is about the same as, or relatively smaller than the outside diameter of a fiber, preferably from about 0.5 d to 1 d thick, which becomes the spacing between adjacent outside surfaces of fibers in successive linear arrays.
[0099] Having formed a first array, a second array (not shown because it would appear essentially identical to the first) is prepared in a manner analogous to the first, strip 15 of the second array is overlaid upon the intermediate portions 12 ′ on strip 15 of the first array, the strip 15 of the second array resting on the upper surfaces of the fibers secured in strip 15 of the first array. Similarly, strip 16 of the second array is overlaid upon the intermediate portions 12 ′ on strip 16 of the first array.
[0100] A third array (essentially identical to the first and second) is prepared in a manner analogous to the first, and then overlaid upon the second, with the strips of the third array resting on the upper surfaces of the fibers of the second array.
[0101] Additional arrays are overlaid until the desired number of arrays are stacked in rows forming a stack of arrays with the adhesive-coated strips forming the spacing means between successive rows of fibers. The stack of arrays on strips is then held vertically to present the lower portion of the stack to be potted first.
[0102] Referring to FIG. 4 , there is schematically illustrated a rectangular potting pan 17 the length and width dimensions of which correspond substantially to the longitudinal (x-axis) and transverse (y-axis) dimensions respectively, of the desired header. The lower stack is submerged in a first liquid which rises to a level indicated by L 1 , in the pan 17 . Most preferred is a liquid wax, preferably a water-soluble wax having a melting point lower than 75° C., such as a polyethylene glycol (PEG) wax.
[0103] The depth to which the first liquid is poured will depend upon whether the strips 15 are to be removed from, or left in the finished header.
[0104] A. First illustrated is the potting of skein fibers in upper and lower headers from which the strips will be removed.
[0105] (1) A first shaped lamina having a thickness L 1 (corresponding to the depth to which the first liquid was poured) is formed to provide a fugitive lamina from about 5-10 cm thick. The depth of the first liquid is sufficient to ensure that both the intermediate portions 12 ′ on the strips and terminal portions 12 ″ will be held spaced apart when the first liquid solidifies and plugs all the fibers.
[0106] (2) The second liquid, a curable, water-insoluble liquid potting resin, or reactive components thereof, is poured over the surface of the fugitive lamina to surround the fibers, until the second liquid rises to a level L 2 . It is solidified to form the fixing lamina (which will be the finished header) having a thickness measured from the level L 1 to the level L 2 (the thickness is written “L 1 -L 2 ″). The thickness L 1 -L 2 of the fixing lamina, typically from about 1 cm to about 5 cm, is sufficient to maintain the relative positions of the vertical fibers. A first composite header is thus formed having the combined thicknesses of the fugitive and fixing laminae.
[0107] (3) In a manner analogous to that described immediately hereinabove, a stack is potted in a second composite header.
[0108] (4) The composite headers are demolded from their potting pans and hot air blown over them to melt the fugitive laminae, leaving only the finished headers, each having a thickness L 1 -L 2 . The fugitive material such as the PEG wax, is then reused. Alternatively, a water-soluble fugitive material may be placed in hot water to dissolve the wax, and the material recovered from its water solution.
[0109] (5) The adhered strips and terminal portions of the fibers which were embedded within the fugitive lamina are left protruding from the permeate-discharging aft faces of the headers with the ends of the fibers being not only open, but essentially circular in cross section. The fibers may now be cut above the strips to discard them and the terminal portions of the fibers adhered to them, yet maintaining the circular open ends. The packing density of fibers, that is, the number of fibers per unit area of header preferably ranges from 4 to 50 fibers/cm 2 depending upon the diameters of the fibers.
[0110] B. Illustrated second is the potting of skein fibers in upper and lower headers from which the strips will not be removed, to avoid the step of cutting the fibers.
[0111] (1) The first liquid is poured to a level L 1 ′ below the cards, to a depth in the range from about 1-2.5 cm, and solidified, forming fugitive lamina L 1 ′.
[0112] (2) The second liquid is then poured over the fugitive lamina to depth L 2 and solidified, forming a composite header with a fixing lamina having a thickness L 1 ′-L 2 .
[0113] (3) The composite header is demolded and the fugitive lamina removed, leaving the terminal portions 12 ″ protruding from the aft face of the finished header, which aft face is formed at what had been the level L 1 ′. The finished header having a thickness L 1 ′-L 2 embeds the strips 15 (along with the rubber bands 18 , if used).
[0114] C. Illustrated third is the potting of skein fibers to form a finished headers with a cushioning lamina embedding the fibers on the opposed (fore) faces of the headers from which the strips will be removed.
[0115] The restricted swayability of the fibers generates some intermittent ‘snapping’ motion of the fibers. This motion has been found to break the potted fibers around their circumferences, at the interface of the fore face and substrate. The hardness of the fixing material which forms a “fixing lamina” was found to initiate excessive shearing forces at the circumference of the fiber. The deleterious effects of such forces is minimized by providing a cushioning lamina of material softer than the fixing lamina. Such a cushioning lamina is formed integrally with the fixing lamina, by pouring cushioning liquid (so termed for its function when cured) over the fixing lamina to a depth L 3 as shown in FIG. 4 , which depth is sufficient to provide enough ‘give’ around the circumferences of the fibers to minimize the risk of shearing. Such cushioning liquid, when cured is rubbery, having a hardness in the range from about Shore A 30 to Shore D 45 , and is preferably a polyurethane or silicone or other rubbery material which will adhere to the fixing lamina. Upon removal of the fugitive lamina, the finished header thus formed has the combined thicknesses of the fixing lamina and the cushioning lamina, namely L 1 -L 3 when the strips 15 are cut away.
[0116] D. Illustrated fourth is the formation a finished header with a gasketing lamina embedding the fibers on the header's aft face, and a cushioning lamina embedding the fibers on the header's fore face; the strips are to be removed.
[0117] Whichever finished header is made, it is preferably fitted into a permeate pan 20 as illustrated in FIG. 2 with a peripheral gasket. It has been found that it is easier to seal the pan against a gasketing lamina, than against a peripheral narrow gasket. A relatively soft gasketing material having a hardness in the range from Shore A 40 to Shore D 45 , is desirable to form a gasketing lamina integrally with the aft face of the finished header. In the embodiment in which the strips are cut away, the fugitive lamina is formed as before, and a gasketing liquid (so termed because it forms the gasket when cured) is poured over the surface of the fugitive lamina to a depth L 4 . The gasketing liquid is then cured. Upon removal of the fugitive lamina, when the strips 15 are cut away, the finished header thus formed has the combined thicknesses of the gasketing lamina (L 1 -L 4 ), the fixing lamina (L 4 -L 2 ) and the cushioning lamina (L 2 -L 3 ), namely an overall L 1 -L 3 .
[0118] In another embodiment, to avoid securing the pan to the header with a gasketing means, and, to avoid positioning one or more gas-distribution manifolds in an optimum location near the base of the skein fibers after a skein is made, the manifolds are formed integrally with a header. Referring to FIG. 5 there is illustrated in perspective view an “integral single skein” referred to generally by reference numeral 100 . The integral single skein is so termed because it includes an integral finished header 101 and permeate pan 102 . The pan 102 is provided with a permeate withdrawal nipple 106 , and fitted with vertical air-tubes 103 which are to be embedded in the finished header. The air-tubes are preferably manifolded on either side of the skein fibers, to feeder air-tubes 104 and 105 which are snugly inserted through grommets in the walls of the pan. The permeate nipple 106 is then plugged, and a stack of arrays is held vertically in the pan in which a fugitive lamina is formed embedding both the ends of the fibers and the lower portion of the vertical air-tubes 103 . A fixing lamina is then formed over the fugitive lamina, embedding the fibers to form a fixing lamina through which protrude the open ends of the air-tubes 103 . The fugitive lamina is then melted and withdrawn through the nipple 106 . In operation, permeate collects in the permeate pan and is withdrawn through nipple 106 .
[0119] FIG. 6 illustrates a cross-section of an integral single skein 110 with another integral finished header 101 having a thickness L 1 -L 2 , but without a cushioning lamina, formed in a procedure similar to that described hereinabove. A permeate pan 120 with outwardly flared sides 120 ′ and transversely spaced-apart through-apertures therein, is prefabricated between side walls 111 and 112 so the pan is spaced above the bottom of the reservoir.
[0120] A pair of air-manifolds 107 such as shown in FIG. 7A or 7 B, is positioned and held in mirror-image relationship with each other adjacent the permeate pan 120 , with the vertical air-tubes 103 protruding through the apertures in sides 120 ′, and the ends 104 and 105 protrude from through-passages in the vertical walls on either side of the permeate pan. Permeate withdrawal nipple 106 ( FIG. 6 ) is first temporarily plugged. The stack of strips 15 is positioned between air-tubes 103 , vertically in the pan 120 which is filled to level L 1 to form a fugitive lamina, the level being just beneath the lower edges of the strips 15 which will not be removed. When solidified, the fugitive lamina embeds the terminal portions of the fibers 12 and also fills permeate tube 106 . Then the second liquid is poured over the upper surface of the fugitive lamina until the liquid covers the strips 15 but leaves the upper ends of the air-tubes 103 open. The second liquid is then cured to form the fixing lamina of the composite header which is then heated to remove the fugitive material through the permeate nozzle 106 after it is unplugged.
[0121] FIG. 7A schematically shows in perspective view, an air-manifold 107 having vertical air-tubes 103 rising from a transverse header-tube which has longitudinally projecting feeder air-tubes 104 and 105 . The bore of the air-tubes which may be either “fine bubble diffusers”, or “coarse bubble diffusers”, or “aerators”, is chosen to provide bubbles of the desired diameter under operating conditions, the bore typically being in the range from 0.1 mm to 5 mm. Bubbles of smaller diameter are preferably provided with a perforated transverse tube 103 ′ of an air-manifold 107 ′ having feeder air-tubes 104 ′ and 105 ′, illustrated in FIG. 7B . In each case, the bubbles function as a mechanical brush.
[0122] The skein fibers for the upper header of the skein are potted in a manner analogous to that described above in a similar permeate pan to form a finished header, except that no air manifolds are inserted.
[0123] Referring to FIG. 8 there is schematically illustrated, in a cross-sectional perspective view, an embodiment in which a bank of two skeins is potted in a single integral finished header enclosure, referred to generally by reference numeral 120 b . The term “header enclosure” is used because its side walls 121 and 122 , and end walls (not shown) enclose a plenum in which air is introduced. Instead of a permeate pan, permeate is collected from a permeate manifold which serves both skeins. Another similar upper enclosure 120 u (not shown), except that it is a flat-bottomed channel-shaped pan (inverted for use as the upper header) with no air-tubes molded in it, has the opposed terminal portions of all the skein fibers potted in the pan. For operation, both the lower and upper enclosures 126 b and 120 u , with their skein fibers are lowered into a reservoir of the substrate to be filtered. The side walls 121 and 122 need not rest on the bottom of the reservoir, but may be mounted on a side wall of the reservoir.
[0124] The side walls 121 and 122 and end walls are part of an integrally molded assembly having a platform 123 connecting the walls, and there are aligned multiple risers 124 molded into the platform. The risers resemble an inverted test-tube, the diameter of which need only be large enough to have an air-tube 127 inserted through the top 125 of the inverted test-tube. As illustrated, it is preferred to have “n+1” rows of air-tubes for “n” stacks of arrays to be potted. Crenelated platform 123 includes risers 124 between which lie channels 128 and 129 . Channels 128 and 129 are each wide enough to accept a stack of arrays of fibers 12 , and the risers are wide enough to have air-tubes 127 of sufficient length inserted therethrough so that the upper open ends 133 of the air-tubes protrude from the upper surface of the fixing material 101 . The lower ends 134 of the air-tubes are sectioned at an angle to minimize plugging, and positioned above the surface S of the substrate. The channel 129 is formed so as to provide a permeate withdrawal tube 126 integrally formed with the platform 123 . Side wall 122 is provided with an air-nipple 130 through which air is introduced into the plenum formed by the walls of the enclosure 120 b , and the surface S of substrate under the platform 123 . Each stack is potted as described in relation to FIG. 6 above, most preferably by forming a composite header of fugitive PEG wax and epoxy resin around the stacks of arrays positioned between the rows of risers 124 , making sure the open ends of the air-tubes are above the epoxy fixing material, and melting out the wax through the permeate withdrawal tube 126 . When air is introduced into the enclosure the air will be distributed through the air-tubes between and around the skeins.
[0125] Referring to FIG. 9 there is shown a schematic illustration of a skein having upper and lower headers 41 u and 41 b respectively, and in each, the protruding upper and lower ends 12 u ″ and 12 b ″ are evidence that the face of the header was not cut to expose the fibers. The height of the contiguous intermediate portions 12 u ′ and 12 b ′ respectively, corresponds to the cured depth of the fixing material.
[0126] It will now be evident that the essential feature of the foregoing potting method is that a fugitive lamina is formed which embeds the openings of the terminal portions of the fibers before their contiguous intermediate portions 12 u ′ and 12 u ” and 12 b ′ and 12 b ″ respectively are fixed in a fixing lamina of the header. An alternative choice of materials is the use of a fugitive potting compound which is soluble in a non-aqueous liquid in which the fixing material is not soluble. Still another choice is to use a water-insoluble fugitive material which is also insoluble in non-aqueous liquids typically used as solvents, but which fugitive material has a lower melting point than the final potting material which may or may not be water-soluble.
[0127] The fugitive material is inert relative to both, the material of the fibers as well as the final potting material to be cast, and the fugitive material and fixing material are mutually insoluble. Preferably the fugitive material forms a substantially smooth-surfaced solid, but it is critical that the fugitive material be at least partially cured, sufficiently to maintain the shape of the header, and remain a solid above a temperature at which the fixing material is introduced into the header mold. The fugitive lamina is essentially inert and insoluble in the final potting material, so that the fugitive lamina is removably adhered to the fixing lamina.
[0128] The demolded header is either heated or solvent extracted to remove the fugitive lamina. Typically, the fixing material is cured to a firm solid mass at a first curing temperature no higher than the melting point or Tg of the fugitive lamina, and preferably at a temperature lower than about 60.degree. C.; the firm solid is then post-cured at a temperature high enough to melt the fugitive material but not high enough to adversely affect the curing of the fixing material or the properties of the fibers. The fugitive material is removed as described hereinafter, the method of removal depending upon the fugitive material and the curing temperature of the final potting material used.
[0129] Since, during operation, a high flux is normally maintained if cleansing air contacts substantially all the fibers, it will be evident that when it is desirable to have a skein having a cross-section which is other than generally rectangular, for example elliptical or circular, or having a geometrically irregular periphery, and it is desired to have a large number of skein fibers, it will be evident that the procedure for stacking consecutive peripheral arrays described above will be modified. Further, the transverse central air-tube 52 (see FIG. 9 ) is found to be less effective in skeins of non-rectangular cross-section than a vertical air-tube which discharges air radially along its vertical length and which vertical air-tube concurrently serves as the spacing means. Such skeins with a generally circular or elliptical cross-section with vertical air-tubes are less preferred to form a bank but provide a more efficient use of available space in a reservoir than a rectangular skein.
[0130] Referring further to FIG. 2 , the header 11 has front and rear walls defined by vertical (z-axis) edges 11 ′ and longitudinal (x-axis) edges 13 ′; side walls defined by edges 11 ′ and transverse (y-axis) edges 13 ″; and a base 13 defined by edges 13 ′ and 13 ″.
[0131] The collection pan 20 is sized to snugly accommodate the base 13 above a permeate collection zone within the pan. This is conveniently done by forming a rectangular pan having a base 23 of substantially the same length and width dimensions as the base 13 . The periphery of the pan 20 is provided with a peripheral step as shown in FIG. 2A , in which the wall 20 ′ of the pan terminates in a step section 22 , having a substantially horizontal shoulder 22 ″ and a vertical retaining wall 22 ′.
[0132] FIG. 2B is a bottom plan view of the lower face of header 13 showing the open ends of the fibers 12 ′ prevented from touching each other by potting resin. The geometrical distribution of fibers provides a regular peripheral boundary 14 (shown in dotted outline) which bounds the peripheries of the open ends of the outermost fibers.
[0133] Permeate flows from the open ends of the fibers onto the base 23 of the pan 20 , and flows out of the collection zone through a permeate withdrawal conduit 30 which may be placed in the bottom of the pan in open flow communication with the inner portion of the pan. When the skein is backwashed, back-washing fluid flows through the fibers and into the substrate. If desired, the withdrawal conduit may be positioned in the side of the pan as illustrated by conduit 30 ′. Whether operating under gravity alone, or with a pump to provide additional suction, it will be apparent that a fluid-tight seal is necessary between the periphery of the header 11 and the peripheral step 22 of the pan 20 . Such a seal is obtained by using any conventional means such as a suitable sealing gasket or sealing compound, typically a polyurethane or silicone resin, between the lower periphery of the header 11 and the step 22 . As illustrated in FIG. 2 , permeate drains downward, but it could also be withdrawn from upper permeate port 45 u in the upper permeate pan 43 u (see FIG. 9 ).
[0134] It will now be evident that a header with a circular periphery may be constructed, if desired. Headers with geometries having still other peripheries (for example, an ellipse) may be constructed in an analogous manner, if desired, but rectangular headers are most preferred for ease of construction with multiple linear arrays.
[0135] Referring to FIGS. 9 and 2 A, six rows of fibers 12 are shown on either side of a gas distribution line 52 which traverses the length of the rows along the base of the fibers. The potted terminal end portions 12 b ″ open into permeate pan 43 b . Because portions 12 u ′ and 12 b ′ of individual fibers 12 are potted, and the fibers 12 are preferably from 1% to 2% longer than the fixed distance between upper and lower headers 41 u and 41 b , the fibers between opposed headers are generally parallel to one another, but are particularly parallel near each header. Also held parallel are the terminal end portions 12 u ″ and 12 b ″ of the fibers which protrude from the headers with their open ends exposed. The fibers protrude below the lower face of the bottom header 41 b , and above the upper face of the upper header 41 u . The choice of fiber spacing in the header will determine packing density of the fibers near the headers, but fiber spacing is not a substantial consideration because spacing does not substantially affect specific flux during operation. It will be evident however, that the more fibers, the more tightly packed they will be, giving more surface area.
[0136] Since the length of fibers tends to change while in service, the extent of the change depending upon the particular composition of the fibers, and the spacing between the upper and lower headers is critical it is desirable to mount the headers so that one is adjustable in the vertical direction relative to the other, as indicated by the arrow V. This is conveniently done by attaching the pan 43 u to a plate 19 having vertically spaced apart through-passages 34 through which a threaded stud 35 is inserted and secured with a nut 36 . Threaded stud 35 is in a fixed mounting block 37 .
[0137] The density of fibers in a header is preferably chosen to provide the maximum membrane surface area per unit volume of substrate without adversely affecting the circulation of substrate through the skein. A gas-distribution means 52 such as a perforated air-tube, provides air within the skein so that bubbles of gas (air) rise upwards while clinging to the outer surfaces of the fibers, thus efficiently scrubbing them. If desired, additional air-tubes 52 ′ may be placed on either side of the skein near the lower header 41 b , as illustrated in phantom outline, to provide additional air-scrubbing power. Whether the permeate is withdrawn from the upper header through port 45 u or the lower header through port 45 b , or both, depends upon the particular application, but in all instances, the fibers have a substantially vertical orientation.
[0138] The vertical skein is deployed in a substrate to present a generally vertical profile, but has no structural shape. Such shape as it does have changes continuously, the degree of change depending upon the flexibility of the fibers, their lengths, the overall dimensions of the skein, and the degree of movement imparted to the fibers by the substrate and also by the oxygen-containing gas from the gas-distribution means.
[0139] Referring to FIG. 10 there is illustrated a typical assembly referred to as a “wall-mounted bank” which includes at least two side-by-side skeins, indicated generally by reference numerals 40 and 40 ′ with their fibers 42 and 42 ′; fibers 42 are potted in upper and lower headers 41 u and 41 b respectively; and fibers 42 ′ in headers 41 u ′ and 41 b ′; headers 41 u and 41 b are fitted with permeate collecting means 46 u and 46 b respectively; headers 41 u ′ and 41 b ′ are fitted with permeate collecting means 46 u 40 and 46 b ′ respectively; and, the skeins share a common gas-distribution means 50 . A “bank” of skeins is typically used to retrofit a large, deep tank from which permeate is to be withdrawn using a vacuum pump. In a large reservoir, several banks of skeins may be used in side-by-side relationship within a tank. Each skein includes multiple rows (only one row is shown) of fibers 42 and 42 ′ in upper headers 41 u and 41 u ′, and lower headers 41 b and 41 b ′ respectively, and arms 51 and 51 ′ of gas-distribution means 50 are disposed between the lower headers 41 b and 41 b ′, near their bases. The upper headers 44 u and 44 u ′ are mounted by one of their ends to a vertical interior surface of the wall W of a tank with mounting brackets 53 and 53 ′ and suitable fastening means such as bolts 54 . The wall W thus functions as a spacer means which fixes the distance between the upper and lower headers. Each upper header is provided with a permeate collection pan 43 u and 43 u ′, respectively, connected to permeate withdrawal conduits 45 u and 45 u ′ and manifolded to permeate manifold 46 u through which permeate being filtered into the collection pans is continuously withdrawn. Each header is sealingly bonded around its periphery, to the periphery of each collection pan.
[0140] The skein fibers (only one array of which is shown for clarity) shown in this perspective view have an elongated rectangular parallelpiped shape the sides of which are irregularly shaped when immersed in a substrate, because of the random side-to-side displacement of fibers as they sway. An elongated rectangular parallelpiped shape is preferred since it permits a dense packing of fibers, yet results in excellent scrubbing of the surfaces of the fibers with bubbles. With this shape, a skein may be formed with from 10 to 50 arrays of fibers across the longitudinal width ‘w’ of the headers 41 u , 41 b , and 41 u ′, 41 b ′ with each array having fibers extending along the transverse length ‘l’ of each header. Air-tubes on either side of a skein effectively cleanse the fibers if there are less than about 30 arrays between the air-tubes. A skein having more than 30 arrays is preferably also centrally aerated as illustrated by the air-tube 52 in FIG. 9 .
[0141] Thus, if there are about 100 fibers closely spaced-apart along the transverse length ‘l’ of an array, and there are 25 arrays in a skein in a header of longitudinal width ‘w’, then the opposed terminal end portions of 2500 fibers are potted in headers 41 u and 41 b . The open ends of all fibers in headers 41 b and 41 b ′ point downwards into collection zones in collection pans 43 b and 43 b ′ respectively, and those of all fibers in headers 41 u and 41 u ′ point upwards into collection zones in collection pans 43 u and 43 u ′ respectively. Withdrawal conduits 45 u and 45 u ′ are manifolded to permeate manifold 46 u through which permeate collecting in the upper collection pans 43 u and 43 u ′ is typically continuously withdrawn. If the permeate flow is high enough, it may also be withdrawn from the collection pans 43 b and 43 b ′ through withdrawal conduits 45 b and 45 b ′ which are manifolded to permeate manifold 46 b . When permeate is withdrawn in the same plane as the permeate withdrawal conduits 45 u , 45 u ′ and manifold 46 u , and the transmembrane pressure differential of the fibers is in the range from 35-75 kPa (5-10 psi), manifold 46 u may be connected to the suction side of a centrifugal pump which will provide adequate NPSH.
[0142] In general, the permeate is withdrawn from both the upper and lower headers, until the flux declines to so low a level as to require that the fibers be backwashed. The skeins may be backwashed by introducing a backwashing fluid through the upper permeate collection manifold 46 u , and removing the fluid through the lower manifold 46 b . Typically, from 3 to 30 skeins may be coupled together for internal fluid communication with one and another through the headers, permeate withdrawal means and the fibers; and, for external fluid communication with one another through an air manifold. Since the permeate withdrawal means is also used for backflushing it is generally referred to as a ‘liquid circulation means’, and as a permeate withdrawal means only when it is used to withdraw permeate.
[0143] When deployed in a substrate containing suspended and dissolved organic and inorganic matter, most fibers of organic polymers remain buoyant in a vertical position. The fibers in the skein are floatingly buoyed in the substrate with the ends of the fibers anchored in the headers. This is because (i) the permeate is essentially pure water which has a specific gravity less than that of the substrate, and most polymers from which the fibers are formed also have a specific gravity less than 1, and, (ii) the fibers are buoyed by bubbles which contact them. Fibers made from ceramic, or, glass fibers are heavier than water.
[0144] Adjacent the skeins, an air-distribution manifold 50 is disposed below the base of the bundle of fibers, preferably below the horizontal plane through the horizontal center-lines of the headers. The manifold 50 is preferably split into two foraminous arms 51 and 51 ′ adjacent the bases of headers 41 b and 41 b ′ respectively, so that when air is discharged through holes in each portion 51 and 51 ′, columns of bubbles rise adjacent the ends of the fibers and thereafter flow along the fibers through the skeins. If desired, additional portions (not shown) may be used adjacent the bases of the lower headers but located on the outside of each, so as to provide additional columns of air along the outer surfaces of the fibers.
[0145] The type of gas (air) manifold is not narrowly critical provided it delivers bubbles in a preferred size range from about 1 mm to 25 mm, measured within a distance of from 1 cm to 50 cm from the through-passages generating them. If desired, each portion 51 and 51 ′ may be embedded in the upper surface of each header, and the fibers potted around them, making sure the air-passages in the portions 51 and 51 ′ are not plugged with potting compound. If desired, additional arms of air-tubes may be disposed on each side of each lower header, so that fibers from each header are scrubbed by columns of air rising from either transverse side.
[0146] The air may be provided continuously or intermittently, better results generally being obtained with continuous air flow. The amount of air provided depends upon the type of substrate, the requirements of the type of microorganisms, if any, and the susceptibility of the surfaces of the fibers to be plugged, there always being sufficient air to produce desired growth of the microorganisms when operated in a substrate where maintaining such growth is essential.
[0147] Referring to FIG. 11 , there is schematically illustrated another embodiment of an assembly, referred to as a “stand-alone bank” of skeins, two of which are referenced by numeral 60 . The bank is referred to as being a “stand-alone” because the spacer means between headers is supplied with the skeins, usually because mounting the skeins against the wall of a reservoir is less effective than placing the bank in spaced-apart relationship from a wall. In other respects, the bank 60 is analogous to the wall-mounted bank illustrated in FIG. 10 .
[0148] Each bank 60 with fibers 62 (only a single row of the multiple, regularly spaced apart generally vertical arrays is shown for the sake of clarity) is deployed between upper and lower headers 61 u and 61 b in a substrate ‘S’. The lower headers rest on the floor of the reservoir. The upper headers are secured to rigid vertical air tubes 71 and 71 ′ through which air is introduced into a tubular air manifold identified generally by reference numeral 70 . The manifold 70 includes (i) the vertical tubular arms 71 and 71 ′; (ii) a lower transverse arm 72 which is perforated along the length of the lower header 61 b ′ and secured thereto; the arm 72 communicates with longitudinal tubular arm 73 , and optionally another longitudinal arm 73 ′ (not shown) in mirror-image relationship with arm 73 on the far side of the headers; and (iii) transverse arms 74 and 74 ′ in open communication with 72 and 73; arms 74 and 74 ′ are perforated along the visible transverse faces of the headers 61 b an 61 b ′, and 74 and 74 ′ may communicate with tubular arm 73 ′ if it is provided. The vertical air-tubes 71 and 71 ′ conveniently provide the additional function of a spacer means between the first upper header and the first lower header, and because the remaining headers in the bank are also similarly (not shown) interconnected by rigid conduits, the headers are maintained in vertically and transversely spaced-apart relationship. Since all arms of the air manifold are in open communication with the air supply, it is evident that uniform distribution of air is facilitated.
[0149] As before, headers 61 u and 61 u ′ are each secured in fluid-tight relationship with collection zones in collection pans 63 u and 63 u ′ respectively, and each pan has withdrawal conduits 65 u and 65 u ′ which are manifolded to longitudinal liquid conduits 81 and 81 ′. Analogously, headers 61 b and 61 b ′ are each secured in fluid-tight relationship with collection zones in collection pans 63 b and 63 b ′ respectively, and each pan has withdrawal conduits 65 b and 65 b ′ which are manifolded to longitudinal conduits 82 and 82 ′. As illustrated, withdrawal conduits are shown for both the upper and the lower headers, and both fore and aft the headers. In many instances, permeate is withdrawn from only an upper manifold which is provided on only one side of the upper headers. A lower manifold is provided for backwashing. Backwashing fluid is typically flowed through the upper manifold, through the fibers and into the lower manifold. The additional manifolds on the aft ends of the upper and lower headers not only provides more uniform distribution of backwashing fluid but support for the interconnected headers. It will be evident that, absent the aft interconnecting upper conduit 81 ′, an upper header such as 61 u will require to be spaced from its lower header by some other interconnection to header 61 u ′ or by a spacer strut between headers 61 u and 61 b.
[0150] In the best mode illustrated, each upper header is provided with rigid PVC tubular nipples adapted to be coupled with fittings such as ells and tees to the upper conduits 81 and 81 ′ respectively. Analogously, each lower header is connected to lower conduits 82 and 82 ′ (not shown) and/or spacer struts are provided to provide additional rigidity, depending upon the number of headers to be interconnected. Permeate is withdrawn through an upper conduit, and all piping connections, including the air connection, are made above the liquid level in the reservoir.
[0151] The length of fibers (between headers) in a skein is generally chosen to obtain efficient use of an economical amount of air, so as to maintain optimum flux over a long period of time. Other considerations include the depth of the tank in which the bank is to be deployed, the positioning of the liquid and air manifolds, and the convection patterns within the tank, inter alia.
[0152] In another embodiment of the invention, a bioreactor is retrofitted with plural banks of skeins schematically illustrated in the elevational view shown in FIG. 12 , and the plan view shown in FIG. 13 . The clarifier tank is a large circular tank 90 provided with a vertical, circular outer baffle 91 , a vertical circular inner baffle 92 , and a bottom 93 which slopes towards the center (apex) for drainage of accumulating sludge. Alternatively, the baffles may be individual, closely spaced rectangular plates arranged in outer and inner circles, but continuous cylindrical baffles (shown) are preferred. Irrespective of which baffles are used, the baffles are located so that their bottom peripheries are located at a chosen vertical distance above the bottom. Feed is introduced through feed line 94 in the bottom of the tank 90 until the level of the substrate rises above the outer baffle 91 .
[0153] A bank 60 of plural skeins 10 , analogous to those in the bank depicted in FIG. 10 , each of which skeins is illustrated in FIG. 9 , is deployed against the periphery of the inner wall of the bioreactor with suitable mounting means in an outer annular permeate extraction zone 95 ′ ( FIG. 13 ) formed between the circular outer baffle 91 and the wall of the tank 90 , at a depth sufficient to submerge the fibers. A clarification zone 91 ′ is defined between the outer circular baffle 91 and inner circular baffle 92 . The inner circular baffle 92 provides a vertical axial passage 92 ′ through which substrate is fed into the tank 90 . The skeins form a dense curtain of fibers in radially extending, generally planar vertical arrays as illustrated in FIG. 9 , potted between upper and lower headers 41 u and 41 b . Permeate is withdrawn through manifold 46 u and air is introduced through air-manifold 80 , extending along the inner wall of the tank, and branching out with air-distribution arms between adjacent headers, including outer distribution arms 84 ′ on either side of each lower header 41 b at each end of the bank. The air manifold 80 is positioned between skeins in the permeate extraction zone 95 ′ in such a manner as to have bubbles contact essentially the entire surface of each fiber which is continuously awash with bubbles. Because the fibers are generally vertical, the air is in contact with the surfaces of the fibers longer than if they were arcuate, and the air is used most effectively to maintain a high flux for a longer period of time than would otherwise be maintained.
[0154] It will be evident that if the tank is at ground level, there will be insufficient liquid head to induce a desirable liquid head under gravity alone. Without an adequate siphoning effect, a centrifugal pump may be used to produce the necessary suction. Such a pump should be capable of running dry for a short period, and of maintaining a vacuum on the suction side of from cm ( 10 ″)-51 cm ( 20 ″) of Hg, or −35 kPa (−5 psi) to −70 kPa (−10 psi). Examples of such pumps rated at 18.9 L/min (5 gpm) @ 15 ″ Hg, are (i) flexible-impeller centrifugal pumps, e.g. Jabsco #30510-2003; (ii) air operated diaphragm pumps, e.g. Wilden M2; (iii) progressing cavity pumps, e.g. Ramoy 3561; and (iv) hosepumps, e.g. Waukesha SP 25.
[0155] The skein may also be potted in a header which is not a rectangular prism, preferably in cylindrical upper and lower headers in which substantially concentric arrays of fibers are non-removably potted in cylindrical permeate pans, and the headers are spaced apart by a central gas tube which functions as both the spacer means and the gas-distribution means which is also potted in the headers. As before, the fibers are restrictedly swayable, but permeate is withdrawn from both upper and lower headers through a single permeate pan so that all connections for the skein, when it is vertically submerged, are from above. Permeate is preferably withdrawn from the lower permeate pan through a central permeate withdrawal tube which is centrally axially held within the central gas (air) tube. The concentric arrays are formed by wrapping successive sheets of flat arrays around the central air-tube, and gluing them together before they are potted. This configuration permits the use of more filtration surface area per unit volume of a reservoir, compared to skeins with rectangular prism headers, using the same diameter and length of fibers.
[0156] FIGS. 14-17 specifically illustrate preferred embodiments of the cylindrical vertical skein. Referring to FIG. 14 there is schematically illustrated, in cross-sectional elevational view a vertical cylindrical skein 210 resting on the floor F of a tank, the skein comprising a pair of similar upper and lower cylindrical end-caps 221 and 222 respectively, which serve as permeate collection pans. Bores 226 and 227 in the upper and lower end-caps have permeate withdrawal tubes 231 and 232 , respectively, connected in fluid-tight engagement therein. Permeate withdrawn through the tubes is combined in a permeate withdrawal manifold 230 . Each end-cap has a finished upper/lower header formed directly in it, upper header 223 being substantially identical to lower header 224 . Each header is formed by potting fibers 212 in a potting resin such as a polyurethane or an epoxy of sufficient stiffness to hold and seal the fibers under the conditions of use. A commercially available end-cap for poly (vinyl chloride) “PVC” pipe is most preferred; for large surface area skeins, larger headers are provided by commercially available glass fiber reinforced end-caps for cylindrical tanks. It is essential that the fibers are not in contact with each other, but spaced apart by cured resin. It is also essential that the cured resin adhere to and seal the lower portions 212 ′ of each of the fibers against leakage of fluid under operating conditions of the skein. Visual confirmation of a seal is afforded by the peripheries of the fibers being sealed at the upper (fore) and lower (aft) faces 223 u and 223 b respectively of the upper header 223 , and the fore and aft faces 224 u and 224 b respectively of the lower header 224 . A conventional finished header may be used in which the ends 212 ″ of the fibers would be flush (in substantially the same plane) as the lower face 224 b . In the best mode, though not visible through an opaque end-cap, the open ends 212 ″ of the fibers protrude from the headers' lower (aft or bottom) face 224 b.
[0157] The finished upper header 223 (fixing lamina) is left adhered to the periphery of the end-cap 221 when the fugitive lamina is removed through bore 226 in the upper header; and analogously, the finished lower header 224 is left adhered to the periphery of the end-cap 222 when the fugitive lamina is removed through a bore 227 .
[0158] Skein fibers 212 are preferably in arrays bundled in a geometric configuration such as a spiral roll. A header is formed in a manner analogous to that described in relation to FIG. 4 , by potting the lower end of the spiral roll. FIG. 14A , showing a bottom plan view of the aft face 224 b of header 224 , illustrates the spiral pattern of openings in the ends 212 ″ of the fibers. It is preferred, before an array is rolled into a spiral, to place a sparger 240 (shown in FIG. 15A ) with a rigid air-supply tube 242 in the array so that upon forming a spiral roll the air-supply tube is centrally axially held within the roll.
[0159] Illustrated in FIG. 14B is a bottom plan view of aft face 224 b with another configuration, wherein a series of successively larger diameter circular arrays are formed, each a small predetermined amount larger than the preceding one, and the arrays secured, preferably adhesively, one to the next, near their upper and lower peripheries respectively to form a dense cylindrical mass of fibers. In such a mass of fibers, referred to as a series of annular rings, each array is secured both to a contiguous array having a next smaller diameter, as well as to a contiguous array having a next larger diameter, except for the innermost and outermost arrays which have the smallest and largest diameters, respectively. The pattern in header 224 illustrates the ends 212 ″ of the fibers after the nested arrays are potted.
[0160] Illustrated in FIG. 14C is a bottom plan view of lower (aft) face 224 b with plural arrays arranged chord-like within the header 224 . Arrays are formed on pairs of strips, each having a length corresponding to its position as a chord within a potting ring in which the skein fibers are to be potted. That is, each array is formed on strips of diminishing width, measured from the central array which is formed on a strip having a width slightly less than the inner diameter of the potting ring in which the stack is to be potted. The arrays are stacked within the ring, the widest array corresponding in position to the diameter of the ring. For a chosen fiber 212 , the larger the surface area required in a skeins the greater the number of fibers in each array, the bigger the diameter of the ring, and the wider each chord-like array. The plural arrays are preferably adhered one to the other by coating the surfaces of fibers with adhesive prior to placing a strip of the successive array on the fibers. Alternatively, the bundled arrays may be held with a rubber band before being inserted in the potting ring. The resulting chord-like pattern in header 224 illustrates the ends 212 ″ of the fibers after the nested arrays are potted.
[0161] A detail of a sparger 240 is provided in FIG. 15A . The star-shaped sparger 240 having radially outwardly extending tubular arms 241 and a central supply stub 242 , supplies air which is directed into the tubular arms and discharged into the substrate through air passages 43 in the walls of the arms. An air feed tube 244 connected to the central supply stub 242 provides air to the sparger 240 . The lower end of the central stub 242 is provided with short projecting nipples 245 the inner ends of which are brazed to the stub. The outer ends of the nipples are threaded. The central stub and nipples are easy to insert into the center of the mass of skein fibers. When centrally positioned, arms 241 which are threaded at one end, are threadedly secured to the outer ends of the nipples.
[0162] As illustrated in FIG. 14 , lower end-cap 222 rests on the floor F of a tank, near a vertical wall W to which is secured a vertical mounting strut 252 with appropriate fastening means such as a nut 253 and bolt 254 . A U-shaped bracket 251 extends laterally from the base of the mounting strut 252 . The arms of the U-shaped bracket support the periphery of upper end-cap 221 , and to ensure that the end-cap stays in position, it is secured to the U-shaped bracket with a right angle bracket and fastening means (not shown). A slot in mounting strut 252 permits the U-shaped bracket to be raised or lowered so that the desired distance between the opposed faces 223 b and 224 u of the upper and lower headers respectively is less than the length of any potted fiber, measured between those faces, by a desired amount. Adjustability is particularly desirable if the length of the fibers tends to change during service.
[0163] As illustrated in FIG. 14 , if it is desirable to withdraw permeate from only the upper tube 231 , a permeate connector tube 233 (shown in phantom outline), is inserted within the mass of skein fibers 212 through the headers 223 and 224 , connecting the permeate collection zone 229 in the lower end-cap in open fluid communication with the permeate collection zone 228 in the upper end-cap; and, bore 227 is plugged with a plug 225 as shown in FIG. 15 . As illustrated in FIG. 15 , in the event that withdrawal of permeate from the upper permeate collection zone 228 alone is sufficient, and it is unnecessary to withdraw permeate from both the upper and lower zones 228 and 229 , the lower bore 227 of the lower end-cap 222 is simply plugged with a plug 225 . Since, under such circumstances, it does not matter if the lower ends 212 ″ of the fibers are plugged, and permeate collection zone 229 serves no essential function, the zone 229 may be filled with potting resin.
[0164] Referring to FIG. 16 there is illustrated a skein 270 with upper and lower end-caps in which are sealed upper and lower ring headers formed in upper and lower rings 220 u and 226 b respectively, after the fibers in the skein are tested to determine if any is defective. A rigid air-supply tube 245 is positioned in the spiral roll as described above, and the lower end of the roll is potted forming a lower finished header 274 in which the lower end 246 of the air-supply tube is potted, fixing the position of the arms 241 of the sparger just above the upper face 274 u of the header 274 .
[0165] In an analogous manner, an upper header 273 is formed in ring 220 u and upper end 247 of air-supply tube 245 is inserted through an axial bore 248 within upper end-cap 271 which is slipped over the ring 220 u the outer periphery of which is coated with a suitable adhesive, to seal the ring 220 u in the end-cap 271 . The periphery of the upper end 247 is sealed in the end cap 271 with any conventional sealing compound.
[0166] Referring to FIG. 17 there is schematically illustrated another embodiment of a skein 280 in which rigid permeate tube 285 is held concentrically within a rigid air-supply tube 286 which is potted axially within skein fibers 212 held between opposed upper and lower headers 283 and 284 in upper and lower rings 220 u and 226 b which are in turn sealed in end-caps 281 and 282 respectively. For ease of manufacture, the lower end 285 b of permeate tube 285 is snugly fitted and sealed in a bushing 287 . The bushing 287 and end 285 b are then inserted in the lower end 286 b of the air supply tube 286 and sealed in it so that the annular zone between the outer surface of permeate tube 285 and the inner surface of air supply tube 286 will duct air to the base of the fibers but not permit permeate to enter the annular zone. The air supply tube is then placed on an array and the array is rolled into a spiral which is held at each end with rubber bands. The lower end of the roll is placed in a ring 226 b and a lower ring header is formed with a finished header 284 as described above. It is preferred to use a relatively stiff elastomer having a hardness in the range from 50 Shore A to about 20 Shore D, and most preferred to use a polyurethane having a hardness in the range from 50 Shore A to about 20 Shore D, measured as set forth in ASTM D-790, such as PTU-921 available from Canadian Poly-Tech Systems. To form the upper finished header 283 the air supply tube is snugly inserted through an O-ring held in a central bore in a plate such as used in FIG. 5 , to avoid loss of potting resin from the ring, and the fugitive resin and finishing resins poured and cured, first one then the other, in the ring. Lower finished header 284 is formed with intermediate portions 212 b ′ embedded, and terminal portions 212 b ″ protruding from the header's aft face. Upper finished header 283 is formed with intermediate portions 212 u ′ embedded, and terminal portion 212 u ″ protruding from the header's fore face. After the finished headers 283 and 284 are formed and the fibers checked for defects, the upper end 286 u of the air supply tube 286 is inserted through a central bore 288 in upper end-cap 281 and sealed within the bore with sealing compound or a collar 289 . Preferably the permeate tube 285 , the air supply tube 286 and the collar 289 are all made of PVC so that they are easily cemented together to make leak-proof connections.
[0167] As shown, permeate may be withdrawn through the permeate tube 285 from the permeate collection zone in the lower end-cap 282 , and separately from the upper end-cap 281 through permeate withdrawal port 281 p which may be threaded for attaching a pipe fitting. Alternatively, the permeate port 281 p may be plugged and permeate withdrawn from both end-caps through the permeate tube 285 .
[0168] Upper end 285 u and upper end 286 u of air supply tube 286 are inserted through a T-fitting 201 through which air is supplied to the air supply tube 286 . The lower end 201 b of one of the arms of the T 201 is slip-fitted and sealed around the air supply tube. The upper end 201 u of the other arm is inserted in a reducing bushing 202 and sealed around the permeate tube. Air supplied to intake 203 of the T 201 travels down the annular zone between the permeate tube and the air supply tube and exits through opposed ports 204 in the lower portion of the air supply tube, just above the upper face 284 u of the lower header 284 . It is preferred to thread ports 204 to threadedly secure the ends of arms 241 to form a sparger which distributes air substantially uniformly across and above the surface 284 u . Additional ports may be provided along the length of the vertical air supply tube, if desired.
EXAMPLE 1
[0169] Microfiltration of an activated sludge at 30° C. having a concentration of 25 g/L (2.5% TSS) is carried out with a skein of polysulfone fibers in a pilot plant tank. The fibers are “air scrubbed” at a flow rate of 12 CFM (0.34 m 3 /min) with a coarse bubble diffuser generating bubbles in the range from about 5 mm to 25 mm in nominal diameter. The air is sufficient no only for the oxidation requirements of the biomass but also for adequate scrubbing. The fibers have an outside diameter of 1.7 mm, a wall thickness of about 0.5 mm, and a surface porosity in the range from about 20% to 40% with pores about 0.2 μm in diameter, both latter physical properties being determined by a molecular weight cut off at 200,000 Daltons. The skein which has 1440 fibers with a surface area of 12 m 2 is wall-mounted in the tank, the vertical spaced apart distance of the headers being about 1% less than the length of a fiber in the skein. The opposed ends of the fibers are potted in upper and lower headers respectively, each about 41 cm long and 10 cm wide. The fixing material of the headers is an epoxy having a hardness of about 70 Shore D with additional upper and lower laminae of softer polyurethane (about 60 shore A and 30 Shore D respectively) above and below the epoxy lamina, and the fibers are potted to a depth sufficient to have their open ends protrude from the bottom of the header. The average transmembrane pressure differential is about 34.5 kPA (5 psi). Permeate is withdrawn through lines connected to the collection pan of each header with a pump generating about 34.5 kPa (5 psi) suction. Permeate is withdrawn at a specific flux of about 0.7 lm 2 h/kPa yielding about 4.8 I/min of permeate which has an average turbidity of <0.8 NTU, which is a turbidity not discernible to the naked eye.
EXAMPLE 2
Comparison of Operation of a Vertical Skein (ZW 72) in Different Orientations
[0170] In the following comparison, three pairs of identical skeins with equally slack fibers are variously positioned (as designated) above aerators in a bioreactor. Each pair is subjected to the same discharge of air through identical aerators. Rectangular but not square headers are chosen to determine whether there is a difference between each of two flat horizontal orientations, which difference would not exist in a horizontal skein with cylindrical headers. A pair of identical rectangular skeins, each having headers 41.66 cm (16.4 in) in length (x-axis), 10.16 cm (4 in) in width (y-axis) and 7.62 cm (3 in) in height (z-axis), in which are potted 1296 Zenon.RTM. MF200 microfiltration fibers presenting a nominal fiber surface area of 625 m 2 , were tested in three different orientations in a bioreactor treating domestic wastewaters. The fibers used are the same as those used in Example 1 above. The distance between opposed faces of headers is 90 cm (35.4 in) which is about 2% less than the length of each fiber potted in those headers.
[0171] In a first test, the two (first and second) skeins were stacked laterally, each in the same direction along the longitudinal axis, with a 2.5 cm ( 1 in) thick spacer between the headers, the headers of each skein being in a horizontal flat orientation (area 41.66 cm×7.62 cm) is spaced apart 7.62 cm ( 3 in) above the floor on which lies the aerators in the form of three side-by-side linear tubes with 3 mm (0.125″) openings. The first skein which is directly above the aerators is therefore referred to as the “lower skein”.
[0172] In a second test, the same first and second skeins are each rotated 90° about the longitudinal x-axis and placed contiguously one beside the other. In this “horizontal 90°” orientation (area defined by 10.16 cm×7.62 cm) is spaced apart from the aerators as in the prior test.
[0173] In a third test, the first and second skeins are placed side-by-side in vertical orientations as shown in FIG. 9 except there is no internal aerator.
[0174] Each test provides the fibers in each orientation with the identical amount of air. Permeate was withdrawn with a pump with a NPSH of 0.3 bar ( 10 ″ of Hg). The conditions were held constant until it was observed that the flux obtained for each test was substantially constant, this being the equilibrium value. After this occurred, each skein was back pulsed for 30 sec with permeate every 5 minutes to maintain the flux at the equilibrium value.
[0175] The test conditions for each of the above three runs were as follows:
TSS in bioreactor 8 g/L; Temperature of biomass 19° C. Flow rate of air 0.2124 m 3 /min/skein; Suction on fibers 25.4 cm of Hg
[0176] FIG. 18 is a bar graph which shows the average flux over a 24 hr period for each orientation of the skein as follows:
Average flux Orientation L/m 2 /hr over 24 hr Horizontal flat 21.2 LMH Horizontal 90° 17.8 LMH Vertical 27.7 LMH
[0177] This conclusively demonstrates that the vertical orientation of the skein fibers produces the highest overall flux.
EXAMPLE 3
Comparison of Positions of Aerator Inside and Outside the Skein Fibers
[0178] In this test the difference in flux is measured in a bioreactor treating wastewater contaminated with ethylene glycol, the difference depending upon how a single cylindrical vertical skein (ZW 172) having a nominal surface area of 16 m 2 is aerated with 3.5 L/min (7.5 scfn). The skein is formed as shown in FIG. 16 around a central PVC pipe having an o.d. of 75 cm, the fibers being disposed in an annular zone around the central support, the radial width of the annular zone being about 75 cm, so that the o.d. of the skein is about 11.25 cm.
[0179] In a first test, air is introduced within the skein; in a second test, air is introduced around the periphery of the skein. After equilibrium is reached, operation is typically continued by back pulsing the skein with permeate at chosen intervals of time, the interval depending upon how quickly the fibers foul sufficiently to decrease the flux substantially.
[0180] The process conditions, which were held constant over the period of the test, were as follows:
TSS 17 g/L; Temperature of biomass 10.5° C. Flow rate of air 0.2124 m 3 /min; Suction on fibers 25.4 cm of Hg
[0181] For external aeration: A perforated flexible tube with holes about 3 mm in diameter spaced about 2.5 cm apart was wrapped around the base of the ZW 72 skein and oriented so that air is discharged in a horizontal plane, so that bubbles enter laterally into the skein, between fibers. Thereafter the bubbles rise vertically through the skein fibers. Lateral discharge helps keep the holes from plugging prematurely.
[0182] For internal aeration: The central tubular support was used as the central air distribution manifold to duct air into five 4 ″ lengths of ¼″ pipe with ⅛″ holes at 1″ intervals, plugged at one end, in open flow communication with the central pipe, forming a spoke-like sparger within the skein, at the base. The number of holes is about the same as the number in the external aerator, and the flow rate of air is the same. As before the holes discharge the air laterally within the skein, and the air bubbles rise vertically within the skein, and exit the skein below the upper header.
[0183] FIG. 19 is a plot of flux as a function of time, until the flux reaches an equilibrium value. Thereafter the flux may be maintained by back pulsing at regular intervals. As is evident, the equilibrium flux with external aeration is about 2.6 LMH, while the flux with internal aeration is about 9.9 LMH which is nearly a four-fold improvement. From the foregoing it will be evident that, since it is well-known that flux is a function of the flow rate of air, all other conditions being the same during normal operation, a higher flux is obtained with internal aeration with the same flow of air.
EXAMPLE 4
Comparison of Skeins in Which One has Swayable Fibers, the Other Does Not
[0184] The slackness in the fibers is adjusted by decreasing the distance between headers. Essentially no slack is present (fibers are taut) when the headers are spaced at a distance which is the same as the length of a fiber between its opposed potted ends. A single ZW 72 skein is used having a nominal surface area of 6.7 m 2 is used in each test, in a bioreactor to treat wastewater contaminated with ethylene glycol. Aeration is provided as shown in FIG. 9 (no internal aeration) with lateral discharge of air bubbles into the skein fibers through which bubbles rose to the top.
[0185] In the first test the headers are vertically spaced apart so that the fibers are taut and could not sway.
[0186] In the second test, the headers were brought closer by 2 cm causing a 2.5% slackness in each fiber, permitting the slack fibers to sway.
[0187] As before the process conditions, which were held constant over the period of the test, were as follows:
Suspended solids 17 g/L Temperature of biomass 10.5° C. Flow rate of air 0.2124 m 3 /min; Suction on fibers 25.4 cm of Hg
[0188] FIG. 20 is a plot of flux as a function of time, until the flux reaches an equilibrium value. Thereafter the flux may be maintained by back pulsing at regular intervals as before in example 3. As is evident, the equilibrium flux with no swayability is about 11.5 LMH, while the flux with 2.5% slack is about 15.2 LMH, which is about a 30% improvement.
EXAMPLE 5
Filtration of Water With a Vertical Cylindrical Skein to Obtain Clarity
[0189] A cylindrical skein is constructed as in FIG. 16 with Zenon.RTM. MF200 fibers 180 cm long, which provide a surface area of 25 m 2 in cylindrical headers having a diameter of 28 cm held in end-caps having an o.d. of 30 cm. Aeration is provided with a spider having perforated cross-arms with 3 mm (0.125″) dia. openings which discharge about 10 liter/min ( 20 scfm, standard ft 3 /min) of air. This skein is used in four typical applications, the results of which are provided below. In each case, permeate is withdrawn with a centrifugal pump having a NPSH of about 0.3 bar ( 10 ″ Hg), and after equilibrium is reached, the skein is backflushed for 30 sec with permeate every 30 min.
[0190] A. Filtration of Surface (Pond) Water Having 10 mg/L TSS:
[0191] Result—permeate having 0.0 mg/L TSS is withdrawn at a rate of 2000 liters/hr (LPH) with a turbidity of 0.1 NTU. A “5 log” reduction (reduction of original concentration by five orders of magnitude) of bacteria, algae, giardia and cryptosporidium may be obtained, thus providing potable water.
[0192] B. Filtration of Raw Sewage With 100 mg/L TSS:
[0193] Result—permeate having 0.0 mg/L suspended solids is withdrawn at a rate of 1000 LPH (liters/hr) with a turbidity of 0.2 NTU. Plural such skeins may be used in a bank in the full scale treatment of industrial wastewater.
[0194] C. Filtration of a Mineral Suspension Containing 1000 mg/L TSS of Iron Oxide Particles:
[0195] Result—permeate having 0.0 mg/L suspended solids is withdrawn at a rate of 3000 LPH (liters/hr) with a turbidity of 0.1 NTU. High flux is maintained with industrial wastewater containing mineral particles.
[0196] D. Filtration of Fermentation Broth With 10,000 mg/L Bacterial Cells:
[0197] Result—permeate having 0.0 mg/L suspended solids is withdrawn at a rate of 1000 LPH (liters/hr) with a turbidity of 0.1 NTU. The broth with a high biomass concentration is filtered non-destructively to yield the desired permeate, as well as to save living cells for reuse.
EXAMPLE 6
Special Purpose Mini-Skein
[0198] The following examples illustrate the use of a mini-skein for typical specific uses such as filtration of (i) raw sewage to obtain solids-free water samples for calorimetric analyses, (ii) surface water for use in a recreational vehicle (“camper”) or motor home, or (iii) water from a small aquarium for fish or other marine animals.
[0199] A cylindrical mini-skein is constructed as shown in FIG. 16 , with cylindrical headers having an o.d. of 5 cm ( 2 ″) and a thickness of 2 cm (0.75″) with 30 fibers, each 60 cm long to provide a surface area of 0.1 m 2 . The skein is mounted on a base on which is also removably disposed a blower to discharge 15 L/min of air at 12 kPa (3 psig) through a sparger which has 1.6 mm (0.0625″) openings, the air flowing through the skein upwards along the fibers. Also removably mounted on the base is a peristaltic pump which produces a vacuum of 03 bar (10″ Hg). In each application, the self-contained skein with integral permeate pump and gas-discharge means, is placed, for operation, in a cylindrical container of the substrate to be filtered.
[0200] The results with each application (A)-(D) are listed below:
[0201] (i) Raw sewage contains 100 mg/L TSS; permeate containing 0.0 mg/L TSS having a turbidity of O 2 NTU, is withdrawn at 0.1 LPH.
[0202] (ii) Aquarium water withdrawn contains 20 mg/L TSS, including algae, bacteria, fungus and fecal dendritus; permeate containing 0.0 mg/L TSS having a turbidity of 0.2 NTU, is withdrawn at 0.1 LPH.
[0203] (iii) Pond water withdrawn contains 10 mg/L TSS; permeate containing 0.0 mg/L TSS having a turbidity of 0.2 NTU, is withdrawn at 0.1 LPH.
[0204] It will now be evident that the membrane device and basic separation process of this invention may be used in the recovery and separation of a wide variety of commercially significant materials, some of which, illustratively referred to, include the recovery of water from ground water containing micron and submicron particles of siliceous materials, preferably “gas scrubbing” with carbon dioxide; or, the recovery of solvent from paint-contaminated solvent. In each application, the choice of membrane will depend upon the physical characteristics of the materials and the separation desired. The choice of gas will depend on whether oxygen is needed in the substrate.
[0205] In each case, the simple process comprises, disposing a skein of a multiplicity of hollow fiber membranes, or fibers each having a length >0.5 meter, together having a surface area >1 m 2 , in a body of substrate which is unconfined in a modular shell, so that the fibers are essentially restrictedly swayable in the substrate. The substrate is typically not under pressure greater than atmospheric. The fibers have a low transmembrane pressure differential in the range from about 3.5 kPa (0.5 psi) to about 350 kPa (50 psi), and the headers, the terminal portions of the fibers, and the ends of the fibers are disposed in spaced-apart relationship as described herinabove, so that by applying a suction of the aft face of at least one of the headers, preferably both, permeate is withdrawn through the collection means in which each header is mounted in fluid-tight communication.
[0206] Having thus provided a general discussion, and specific illustrations of the best mode of constructing and deploying a membrane device comprising a skein of long fibers in a substrate from which a particular component is to be produced as permeate, how the device is used in a gas-scrubbed skein, and having provided specific illustrative systems and processes in which the skein is used, it is to be understood that no undue restrictions are to be imposed by reason of the specific embodiments illustrated and discussed, and particularly that the invention is not restricted to a slavish adherence to the details set for the herein. | An apparatus is described for withdrawing filtered permeate from a substrate contained in a reservoir at ambient pressure. The apparatus includes a plurality of membrane assemblies. Each assembly has a plurality of hollow fiber filtering membranes, immersed in the reservoir, at least one permeating header with the membranes sealingly secured therein, and a permeate collector to collect the permeate sealingly connected to the at least one permeating header and in fluid communication with lumens of the membranes. The membranes of each assembly extend generally vertically upwards from a first header during permeation. One or more sources of suction are provided in fluid communication with the lumens of the membranes of each assembly through the permeate collectors and apply sufficient suction to withdraw permeate from the lumens of the membranes. An aeration system for discharging bubbles assists in keeping the membranes clean. In other aspects, a method of removing fouling materials from the surface of a plurality of porous membranes includes providing, from within a membrane module, gas bubbles in a uniform distribution relative to the membranes. The bubbles move past the surfaces of the membranes to dislodge fouling materials from them. The membranes are arranged in close proximity to one another and mounted to prevent excessive movement. | 8 |
BACKGROUND OF THE INVENTION
This invention relates to a wireless communication apparatus and method that employ frequency hopping.
In a frequency hopping spread spectrum (FHSS) system, usually a usable frequency band is divided into a plurality of frequency bands (channels) having a fixed bandwidth and the carrier wave of a signal is transmitted while shifting from one channel to another. The particular channels to which a shift is made are given by a hopping pattern (HP). In order to perform communication using the FHSS system, it is required that both the sending and receiving sides have the same hopping pattern and that the system be operated in synchronized fashion. More specifically, demodulation on the receiving side must be performed while changing the reception frequency on the receiving side to follow up the hopping pattern on the sending side. That is, it is required that one and the same hopping pattern be shared by the wireless terminals on the sending and receiving sides in order for communication between the two terminals to be started.
In other words, a wireless terminal possesses only one hopping pattern, which is set when communication starts, and this wireless terminal is capable of communicating only with a specific wireless terminal having the same hopping pattern. Accordingly, in order for a plurality of wireless terminals to communicate with one another simultaneously, communication is carried out by applying time-division multiplexing to communication time based upon the hopping pattern used.
However, a problem arises with this method of communicating. Specifically, when communication time is time-division multiplexed by a single hopping pattern, in the manner mentioned above, in a scenario in which a plurality of wireless terminals communicate simultaneously, this hopping pattern is shared in communication with the other wireless terminals in time-division multiplexing. This means that one wireless terminal cannot communicate simultaneously with these wireless terminals and with another new wireless terminal outside this group.
Further, methods of changing over frequency in conventional wireless communication using frequency hopping include a method of switching frequency every communication frame in accordance with the hopping pattern and a method of switching frequency during the course of a communication frame.
When communication is performed, regardless of the frequency switching method, a communication frame is assembled by adding identification information such as the system ID or individual ID onto the beginning of the communication information and then transmitting the assembled communication frame. The receiving side analyzes the identification information of the received communication frame and accepts the ensuing communication information only if the identification information matches that of the receiving apparatus.
Further, in voice communication, transmission of audio information must be performed in continuous fashion owing to the need for real-time communication. In data communication, however, data cannot be transmitted continuously. In other words, data are transmitted at such time that the data are generated.
Accordingly, another system installed in the neighborhood of one's own apparatus is capable of performing data communication even it is communicating data with this apparatus by using the same hopping pattern. However, another wireless communication apparatus will not recognize the fact that the neighborhood system is communicating using the identical hopping pattern or a hopping pattern in which frequencies are superposed.
Further, with the method of switching frequency in the middle of a communication frame, identification information cannot be added onto all frequencies to which a changeover is made. This means that if an apparatus should happen to receive data transmitted from a system installed in the neighborhood, these data will be received accidentally as data transmitted to that apparatus.
SUMMARY OF THE INVENTION
Accordingly, an object of the present invention is to provide a wireless communication apparatus and method in which one wireless terminal is capable of communicating simultaneously with a plurality of other wireless terminals having a plurality of different hopping patterns.
Another object of the present invention is to provide a wireless communication apparatus and method in which even if another system situated in the neighborhood is communicating at the same frequency, it is possible to avoid receiving the data of this system accidentally.
According to the present invention, the foregoing objects are attained by providing a wireless communication apparatus for time-division multiplexed communication of a plurality of items of information using frequency hopping, comprising means for allocating a plurality of different hopping patterns for each of the plurality of items of information, means for storing the plurality of hopping patterns for each communication, frequency changeover means for changing over frequency for each of the plurality of items of information in accordance with the plurality of hopping patterns stored, and communication means for performing communication at a frequency to which a changeover has been made by the frequency changeover means.
According to the present invention, the foregoing objects are attained by providing a wireless communication method of time-division multiplexed communication of a plurality of items of information using frequency hopping, comprising a step of allocating a plurality of different hopping patterns for each of the plurality of items of information, a step of storing the plurality of hopping patterns for each communication, a frequency changeover step of changing over frequency for each of the plurality of items of information, and a communication step of performing communication at a frequency to which a changeover has been made at the frequency changeover step.
Other features and advantages of the present invention will be apparent from the following description taken in conjunction with the accompanying drawings, in which like reference characters designate the same or similar parts throughout the figures thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagram showing the configuration of a system according to an embodiment of the present invention;
FIG. 2 is a block diagram showing the architecture of a wireless control unit according to the embodiment of the invention;
FIG. 3 is a block diagram showing the architecture of a channel codec according to the embodiment of the invention;
FIG. 4 is a block diagram showing the architecture of a wireless unit in the embodiment of the invention;
FIG. 5 is a diagram showing the structure of a wireless frame in the embodiment of the invention;
FIGS. 6A-6D are diagrams showing the structures of channels in the embodiment of the invention;
FIG. 7 is a diagram showing the example of the structure of a wireless frame;
FIG. 8 is a diagram showing the example of the structure of a wireless frame;
FIG. 9 is a conceptual view showing frequency hopping according to this embodiment;
FIG. 10 shows examples of hopping patterns in the embodiment of the invention;
FIG. 11 is a conceptual view of time-divided channels and frequency hopping;
FIG. 12 is a sequence diagram showing a sequence of operations performed by a control station and a terminal station when power is introduced;
FIG. 13 is a sequence diagram showing a call-control sequence up to the start of transmission;
FIG. 14 is a flowchart of a voice communication control operation according to a first embodiment of the invention;
FIG. 15 is a flowchart of voice communication control according to the first embodiment of the invention;
FIG. 16 is a flowchart of a data communication control operation according to the first embodiment of the invention;
FIG. 17 is a flowchart of a data communication operation according to the first embodiment of the invention;
FIG. 18 is a conceptual view of time-divided channels and frequency hopping at the time of voice communication;
FIG. 19 is a conceptual view of time-divided channels and frequency hopping at the time of data communication;
FIG. 20 is a flowchart of a terminating control operation performed by the control station according to the first embodiment;
FIG. 21 is a flowchart of a terminating control operation performed by a wireless terminal according to the first embodiment;
FIG. 22 is a block diagram showing the architecture of a channel codec according to a second embodiment of the invention;
FIGS. 23A-23E are diagrams showing the structures of wireless frames according to the second embodiment;
FIG. 24 is a flowchart showing a voice communication control operation according to the second embodiment;
FIG. 25 is a flowchart showing a data communication control operation according to the second embodiment;
FIG. 26 is a flowchart showing a data communication operation according to the second embodiment;
FIG. 27 is a flowchart showing a terminating control operation performed by the control station according to the second embodiment; and
FIG. 28 is a flowchart of a terminating control operation performed by a wireless terminal according to the second embodiment.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
First Embodiment
Description of Elements
FIG. 1 is a diagram illustrating the configuration of a wireless communication system according to an embodiment of the invention.
As shown in FIG. 1, the system is composed of wireless terminals having a variety of functions. Shown in FIG. 1 are a public switched telephone network 101, a network controller 102 having a public line interface, a radiotelephone 103, a personal computer 104 to which a wireless PC card (not shown) has been connected, a printer 105 having an internal wireless controller, a wireless LAN adapter 106 having an Ethernet® interface, and a LAN 107.
Any one of these terminals functions as a centralized control station. The terminal serving as the centralized control station generates the reference timing of transmission frames and performs call control and management/allocation of hopping patterns. The other wireless terminals (terminal stations) operate based upon the timing generated by the centralized control station and, at the start of communication, send the centralized control station a transmission request and a request for allocation of a hopping pattern.
FIG. 2 illustrates the architecture of a wireless control unit equipped with a wireless terminal.
As shown in FIG. 2, the unit includes a data input/output interface such as a PCMCIA (personal computer memory card international association) interface, a Centronics interface or an Ethernet® interface, a voice input/output interface such as a handset interface of public switched telephone network interface, an error correction processor (ECC) 203, a CPU 204, a memory 205, a DMA controller 206, an ADPCM codec 207, a channel codec (CHC) 208, a wireless unit 209 and a data bus 210.
By changing the interfaces 201, 202, the wireless control unit can be used as a variety of wireless terminals without changing the construction of the unit.
FIG. 3 is a diagram showing the internal construction of the channel codec of FIG. 2. The channel codec 208 includes a CPU data bus 301, a CPU bus interface 303, an ADPCM interface 304 for dealing with ADPCM-coded voice data 302, an ADPCM interface 304, a mode register 305 for setting operating data, a hopping-pattern register 306 capable of storing a plurality of hopping patterns, a BF/NF register 307 for a frame -- number and/or next frequency number, a system ID register 308, an intermittent start-up terminal address register 309, an LCCH (logical control channel) register 310 for storing control data exchanged with a wireless terminal, an FIFO buffer 311, a timing generator 312 for controlling timing at which wireless link frames are sent and received, a CNT channel assembler/disassembler 313 for performing an exchange of system control data, an LCCH (logical control channel) assembler/disassembler 314, a data assembler/disassembler 315, a voice assembler/disassembler 316, a frame synchronizer 317, a unique-word detector 318, a CRC coder/decoder 319, a bit synchronizer 320, a wireless controller 321, an intermittent reception controller 322, a scrambler/descrambler 323, an AD converter 324, and a reception level detector 325 that outputs an interrupt signal 326. A wireless unit is indicated at 209.
FIG. 4 is a block diagram showing the architecture of the wireless control section within the wireless control unit. The wireless section includes transceiving antennae 401a, 401b, a switch 402 for changing over between the antennae 401a, 401b, a bandpass filter (referred to as a "BPF") 403 for removing signals in unnecessary bands, a switch 404 for switching between transmission and reception, an amplifier 405 for reception, an amplifier (with power controller) 406 for transmission, a down-converter 407 for a first IF (intermediate frequency), an up-converter 408, a switch 409 for switching between transmission and reception, a BPF 410 for eliminating signals in unnecessary bands from the signal converted by the down-converter 407, and a down-converter 411 for a second IF (intermediate frequency). Double-conversion reception is implemented by the down-converters 407 and 411.
The wireless unit further includes a second IF BPF 412, a 90° phase shifter 413, a quadrature detector 414 for detecting and demodulating a signal received by the BPF 412 and phase shifter 413, a comparator 415 for waveshaping, a voltage-controlled oscillator (referred to as a "VCO" below) 416 for reception, a low-pass filter (referred to as an "LPF" below) 417, and a phase-locked loop (referred to as a "PLL") 418 constituted by a programmable counter, prescaler and phase comparator, etc. A frequency synthesizer in the reception loop is constructed by the VCO 416, LPF 417 and PLL 418.
The wireless section further includes a VCO 419 for generating a carrier signal, an LPF 420 and a PLL 421 constituted by a programmable counter, prescaler and phase comparator, etc., which are not shown. A frequency synthesizer for hopping is constructed by the VCO 419, LPF 420 and PLL 421. Further provided are a VCO 422 located in the transmission loop and having a modulating function, an LPF 423, and a PLL 424 constituted by a programmable counter, prescaler and phase comparator, etc., which are not shown. A frequency synthesizer located in the transmission loop and having a frequency modulating function is constructed by the VCO 422, LPF 423 and PLL 424. An oscillator 425 generates a reference clock for the PLLs 418, 421 and 424, and a filter (baseband filter) 426 limits the band of transmission data (the baseband signal).
FIG. 5 is a diagram showing the structure of a wireless frame used in this wireless communication system.
As shown in FIG. 5, the frame includes a system control channel (CNT) 501, a line control channel (LCCH) 502, a voice channel 503 for performing voice communication, a data channel 504 for performing data communication, and guard time (a frequency changeover interval) CF 505 for the purpose of changing frequency. Since the length of one frame is made 10 ms using this low-speed frequency hopping wireless unit whose data transmission speed is 625 Kbps, 6250 bits of information can be sent per frame.
FIGS. 6A-D illustrate the details of each channel. In each channel, CS, CS0, CS1 and CS2 represent carrier sensing times, PR represents preamble time, SYN a frame synchronizing signal, ID an identification code, BF a basic frame number for communicating frame number information used in hopping pattern control, WA a terminal identification number which notifies of cancellation of a sleep mode (i.e., for starting up a terminal during intermittent reception), NF a next hopping frequency (for updating the HP register), Rev a reserve, CRC a redundant bit for error detection, GT guard time, UW a unique word, and DA the terminal identification number of the terminal that is the party to communication. The numerical values below the channel elements indicate the respective numbers of bits.
FIGS. 7 and 8 illustrate other examples of frames. The entirety of the frame in FIG. 7 is for voice channels exclusively. The frame of FIG. 8 is for a data channel exclusively, in which a maximum of 5588 bits of data can be sent per frame. By suitably allocating the 6250 bits of one frame according to each channel, frames in which the number of voice channels and the amount of data communicated in data channels are changed can be used in communication in addition to the frames having the structure described above.
In this embodiment, the CNT channel and LCCH channel use a first hopping pattern as a control channel, two voice data channels use a second hopping pattern and a data channel uses a third hopping pattern.
FIG. 9 is a conceptual view of frequency hopping used in this system.
In the system according to this embodiment, use is made of 26 frequency channels each having a width of 1 MHz, utilizing a frequency band of 26 MHz. Taking into consideration cases in which there are frequencies that cannot be used because of interference noise, 20 frequency channels are selected from the 26 channels and frequency hopping is carried out over the selected frequency channels in a predetermined order.
In this system, one frame has a length of 10 ms and a different frequency channel is hopped every frame. Consequently the length of the period of one hopping pattern is 200 ms.
In FIG. 9, different hopping patterns are indicated by different designs. Patterns in which the same frequencies are not used at the same times are employed by each frame. As a result, it is possible to prevent the occurrence of data errors.
As shown in FIG. 10, in this system control is performed in such a manner that a first hopping pattern (HP1) is used in the CNT and LCCH channels, a second hopping pattern (HP2) is used in the voice channel and a third hopping pattern (HP3) is used in the data channel, as a result of which the channels will not use the same frequency at the same time. This makes it possible to send and receive data to and from a different party per channel.
In order to reduce the number of hopping patterns retained in the channel codec, the hopping patterns used by the respective channels are generated by temporally shifting patterns in which the frequencies are arranged in the same order.
FIG. 11 illustrates the concept of four channels used in this system and the frequency hopping corresponding to each channel. FIG. 11 illustrates the manner in which the control channels, voice channel and data channel undergo hopping independently.
Basic control of the wireless control unit according to this embodiment of the invention will now be described in accordance with FIGS. 2 through 11.
Types of Transmitted Data
The data transmitted in this system are broadly divided into three types.
The first type of data is control data for performing call control such as a transmission request. These data are generated in accordance with a program that has been stored in a ROM. The data are written to the LCCH register 310 in the data codec 208 via the CPU data bus 210.
The second type of data is real-time data such as voice data. These data are entered from the voice input/output interface 202. An analog voice signal is converted to a digital code by the ADPCM codec 207 and is acquired by the channel codec 208 at a predetermined timing.
The third type of data is non-real-time data sent from the memory of a personal computer or the like, by way of example. These data are entered from the data input/output interface 201 and are stored in the memory 205 by DMA transfer under the control of the DMAC 206. When a prescribed amount of these data are stored in the memory 205, coding is applied by the error correction processor (ECC) 203, at which the data are DMA-transferred to the channel codec 208.
It should be noted that when these data are received, the data flow in a manner which is the exact opposite of that described above.
Operation of Channel Codec
The channel codec 208 functions to assemble data in the frame format shown in FIG. 5 and to send data, which have been obtained by disassembling a frame, to the input/output interface 201. The operation of the channel codec 208 will now be described.
First, a reference for the operating timing of the channel codec 208 is generated by the timing generator on the side of the centralized control station described in conjunction with the system of FIG. 1. The centralized control station transmits a frame in accordance with this timing, and a terminal that has received the frame maintains frame synchronization in accordance with the frame synchronizing word within the frame.
Data sent from the centralized control station by way of the CNT channel are stored in a register within the channel codec 208. The channel codec 208 has the HP (hopping-pattern) register 306, the ID register 308 and the WA (start-up terminal address) register 309. On the side of the centralized control station, the internal CPU writes the necessary values to these registers. The value within the BF/NF register 307 for the frame number and/or next frequency number is updated in sync with the operating timing. The frequency number written to the NF register is the hopping pattern (the first hopping pattern) of the CNT channel. The channel codec 208 reads the data out of these registers at the timing at which the data of the CNT channel are transmitted, the data are assembled by the CNT assembler 31 and the assembled data are transmitted.
When the CNT channel is received at the terminal station, the CNT assembler/disassembler 313 disassembles the data of this channel and executes processing using the value contained in each portion of the received channel. More specifically, the terminal station determines whether the received ID matches the value that has been written in its own ID register 308, and control is performed in such a manner that the ensuing data are received only if a match is obtained. In a case where the received WA coincides with the value in its own WA register 309 during intermittent reception, the terminal station generates a start-up request interrupt. Furthermore, the terminal station utilizes the received BF, NF information and rewrites the content of the data contained in the hopping-pattern register 306.
The frequency number that has been written in the NF field of the CNT channel is that of the hopping pattern of the CNT channel. Therefore, the hopping patterns used by the voice channel and data channel are generated by temporally shifting the hopping pattern created based upon the frequency number that has been written in the NF field.
With regard to the LCCH channel, the CPU on the sending side uses the LCCH assembler/disassembler 314 to assemble the data that have been stored in the LCCH register 310 within the channel codec 208. The assembled data are transmitted at the predetermined timing. In order to prevent collision with other terminals, the LCCH channel is provided with a plurality of carrier sensing fields. Further, on the receiving side, the received LCCH channel is disassembled by the LCCH assembler/disassembler 314. Once the disassembled data have been stored in the LCCH register 310, an interrupt is generated and applied to the CPU. In response to the interrupt, the CPU reads the data in the register.
With regard to the voice channel, the channel codec uses the voice assembler/disassembler 316 to assemble data that have entered via the ADPCM interface 304 and transmits the assembled data at the predetermined timing. Conversely, on the receiving side, the received voice channel is disassembled by the voice assembler/disassembler 316 at the predetermined timing and the results are outputted via the ADPCM interface 304 at the timing at which processing is performed in the ADPCM codec 207.
With regard to the data channel, the data are transmitted only if the CPU has requested data transmission. If data transmission has been requested, the CPU bus interface 303 of the channel codec 208 outputs a DMA request to the DMA controller (DMAC) 206 at the timing of every byte. When the DMAC 206 responds to the DMA request and data is written in, the data is converted to a serial one and transmitted at the predetermined timing by the data assembler/disassembler 315. Conversely, in a case where the data channel is received, the data assembler/disassembler 315 converts the data to parallel data and outputs a DMA request to the DMAC 206 byte by byte. The DMA controller 206 transfers the received data to the memory 205. When the transmission of one frame of data ends, an interrupt is generated and applied to the CPU. Upon receiving the interrupt, the CPU executes processing such as processing for acquiring memory for reception of the next frame.
When data are transmitted by all of the above-mentioned channels, the CRC coder 319 generates a CRC code, stores the code in the CRC field and then transmits the result. The CRC is performed on the receiving side and the occurrence of an error is detected. Further, all transmission data other than the frame synchronizing word and unique word are scrambled in the scrambler/descrambler 323. This is to alleviate an imbalance in the transmitted data and to facilitate the extraction of the synchronizing clock.
Conversely, when the frame synchronizing word or unique word is detected at the time data reception, descrambling is carried out in the scrambler/descrambler 323 at the timing at which the word is received, a CRC check is carried out and, at the same time, data are entered disassembled portion of each field.
Example of Operation
In this system as described above, control is such that a frame composed of a plurality of channels for communication between terminals is assembled and the frequency used is changed over at regular time intervals.
The specific operation of this system will be described for a case where a handset connected to a personal computer is used to perform voice communication via the network controller, a case where a personal computer performs a file transfer with another personal computer, and a case where the voice communication and data communication are carried out simultaneously. In this embodiment, the description will be rendered on the assumption that the network controller connected to the public telephone line functions as a centralized control station.
FIG. 12 is a sequence diagram showing a sequence of operations performed by a control station and a terminal station when power is introduced to the system, FIG. 13 is a sequence diagram showing a call-control sequence up to the start of data transmission or voice communication, FIG. 14 is a flowchart of a voice communication control operation in a personal computer, FIG. 15 is a flowchart of operation when voice communication starts, FIG. 16 is a flowchart of a data communication control operation in a personal computer, FIG. 17 is a flowchart of a data communication operation in a personal computer, FIG. 18 is a conceptual view of time-divided channels and frequency hopping at the time of voice communication, and FIG. 19 is a conceptual view of time-divided channels and frequency hopping at the time of data communication.
The invention will now be described in accordance with these FIGS. 12 through 19.
Sequence of Operations by Control Station and Terminal Station at Start-Up
When power is introduced and the terminal is initialized at sequence S1201 in FIG. 12, the terminal determines, based upon the set value in an external switch, whether it is a control station or a terminal station. If the terminal recognizes the fact that it is a control station, then the station decides the first hopping pattern for the control channel, assembles the synchronizing signal, hopping pattern information and its own area number into a frame and outputs the frame as the CNT frame at predetermined timings.
Similarly, when the terminal recognizes, after start-up, that it is a terminal station based upon the set value in the external switch, then the station stores its own address and the received area number of the control station. When this processing ends, the terminal waits for the CNT frame from the control station at any frequency. When the CNT frame from the control station is received, the hopping frequency is acquired in the next unit time based upon NF in this frame. The terminal station changes the reception frequency based upon this frequency and waits for the next CNT frame. This processing is repeated at the terminal station, the hopping pattern being used at the control station is recognized and this hopping frequency is stored in the HP register 306 in the channel codec 208.
When the storing of hopping patterns is finished at the terminal station, the latter uses the LCCH frame at sequence S1202 to notify the control station that it (the terminal station) is being added on as a new terminal station. At this time a global address which will be received by all terminals is included in the DA of the LCCH frame, data indicating that registration is performed anew are included in the data portion of the LCCH frame and then the frame is transmitted. The control station receives the LCCH frame from the terminal station and, if a global address is present in the DA of this frame, receives the data contained in the data portion. If the data contains the address of the terminal station and registration request data, then, on the basis of this address and data, the control station stores the address of the terminal station and registers the address anew as the terminal station.
When registration is finished, the control station notifies the newly registered terminal station of the address of the control station using the LCCH frame at sequence S1203. Upon receiving the address of the control station by way of this LCCH frame, the terminal station stores the address of the control station. When the above-mentioned processing is finished, the terminal station uses the LCCH frame at sequence S1204 to notify the control station of the fact that start-up is completed. Upon receiving this notification of completion of start-up from the terminal station, the control station effects a transition to ordinary processing.
After outputting notification of end of start-up, the terminal station is capable of making a transmission at sequence S1205.
Voice Communication Control
When a transition is made to the transmission control phase (step S1401 in FIG. 14) at the start of voice communication, the terminal station determines whether voice communication has been requested (S1402). If voice communication has been requested ("YES" at step S1402), a personal-computer voice communication application program is started up (see FIG. 13). When this is done, a wireless unit driver that has been installed in the personal computer operates and sends the wireless control unit a voice transmission request and a transmission destination number (the extension number of the other party's terminal) via the data input/output interface (S1403).
Next, the wireless control unit begins a call origination procedure. Specifically, the wireless control unit writes a call origination request command to the LCCH register 310 in the channel codec 208 as LCCH data (S1404), writes the address of the centralized control station to the destination address register (S1405) and then sets the mode register 305 of the channel codec 208 to the LCCH transmission mode (S1406). At the time of LCCT transmission, carrier detection is performed by the carrier sensing field in the channel codec 208 (S1407). If a carrier is detected in this period of time, it may be considered that another terminal is using the LCCH channel. Accordingly, contention control, which involves suspending data transmission until the next frame, is carried out (S1408). If a carrier is not detected, it may be considered that another terminal is not using the LCCH channel. Accordingly, transmission of data to the centralized control station is started (S1409). It should be noted that the hopping pattern used in transmission of the LCCH data is the first hopping pattern, which is the same as that of the CNT channel.
Upon receiving the call origination request command, the centralized control station executes call origination processing, such as dialing a public telephone line. If an answer is received from the called terminal via the public telephone line, a termination notification command is sent, by way of LCCH, to the personal computer that issued the origination request. Furthermore, notification is given of the hopping pattern (the second hopping pattern) which prevails when the voice data are exchanged between the personal computer and the centralized control station, and notification is given of which of the two voice channels is used on the sending side (S1410).
The personal computer, which has received notification of call termination, the hopping pattern and allocation of the channel used, sets the second hopping pattern used by the call communication channel as well as the channel used in the HP register 306 of the channel codec 208 and starts the operation of the ADPCM codec (S1411). As a result, a transition is made to the voice communication phase (S1413). If reception of communication enable is not carried out at S1410, then a busy indication is made at the terminal station (S1412).
With regard to start of a call, the mode register 305 in the channel codec 208 is set to the voice mode (S1501 in FIG. 15), the transmission slot number is set in the mode register (S1502) and the start of operation of the ADPCM codec is set (S1503).
The voice call starts (S1504) and it is determined at S1601 in FIG. 16 whether there is a request for data communication.
By virtue of this procedure, a link is established among the personal computer, the network controller and the other party's terminal and a call between the personal computer and the other party's terminal begins.
During voice communication, the voice that has entered from the handset provided on the personal computer is coded by the ADPCM coder 207, the coded voice data enters the channel codec 208, a preamble and a unique word are added on every 160 bits, and the resulting data are scrambled and then transmitted at the position of the predetermined voice channel.
When bit synchronization is established in the preamble section of the received voice data in the voice channel and the unique word is detected at the time that audio is received, descrambling is carried out. The descrambled data are decoded by the ADPCM codec 207 and the decoded data are outputted as a voice from the speaker of the handset.
At this time the frequency of the control channel is changed over in the manner F1, F2, F3, F4, . . . in accordance with the first hopping pattern, as shown in FIG. 10, and the voice channel changes over the frequency in the manner F3, F4, F5, F6, . . . . Therefore, the changeover of frequency when voice communication is being carried out is as shown in FIG. 18. That is, frequency changeover at the time of voice communication is F1, F3, F2, F4, F3, F5, . . . .
Data Communication Control Operation
If voice communication is not requested at step S1402 in FIG. 14 and the terminal station issues a data communication request at S1601 in FIG. 16 ("YES" at S1601), a data communication application program in a personal computer is started up and a wireless unit driver that has been installed in the personal computer operates and sends the wireless control unit a data transmission request and a transmission destination number (the extension number of the other party's terminal) via the data input/output interface (S1602).
Next, a transition is made to a call origination procedure similar to that executed in the case of voice communication described above (S1603-S1608) and transmission of the LCCH data to the centralized control station begins.
Upon receiving the call origination request command, the centralized control station notifies the other party's terminal of call termination using the LCCH. If an answer is sent back from the other party's terminal, the establishment of the call is completed by sending two terminals the hopping pattern (third hopping pattern) for sending and receiving of data (S1608).
When the two terminals obtain the third hopping pattern for sending/receiving data as the result of the foregoing procedure (S1609), the third hopping pattern used is set in the HP register of the channel codec 208 (S1611). Sending/receiving of data is performed while the frequency is changed over in accordance with the given hopping pattern in the data channel (S1612). More specifically, the driver of the wireless control unit transfers the data transmitted from the memory 205 of the personal computer to the memory 205 of the wireless control unit (S1701), as shown in FIG. 17. If reception of communication enable is not carried out at S1609 in data communication control as well, then a busy indication is presented (S1610).
The wireless control unit subjects the data that has been stored in the memory 205 to error correction coding and stores the coded data in the memory 205 again (S1702). The wireless control unit then sets an address for DMA transfer from the memory 205 to the channel codec 208 in the DMA controller 206 (S1703) and sets a transmission request in the mode register 305 of the channel codec 208 (S1704). Upon receiving the transmission request, the channel codec 208 performs carrier detection (S1705). If a carrier is detected, the channel codec 208 stands by for one frame (S1706). If a carrier is not detected, then the channel codec 208 generates a DMA request in one byte units in conformity with the timing of the data channel. Upon receiving the DMA request, the DMA controller transfers the data in the memory 205 to the channel codec 208 (S1707). The channel codec 208 adds on the preamble and the unique word, scrambles the data and then transmits the scrambled data (S1708).
When transmission of one packet is finished ("YES" at step S1708), an interrupt is generated in the CPU (S1709). If there are data still to be transmitted, then the program returns to step S1703 and transmission processing is executed (S1710).
In a case where there are no data to be transmitted, it is determined whether there is a request for voice communication (S1711). If voice communication has already been carried out, a request for voice communication is not issued anew. However, if only data communication has been carried out and voice communication is requested anew, then the program proceeds to S1402 of FIG. 14.
If voice communication is not requested at S1711, then the mode register 305 in the channel codec 208 is set to the reception mode and reception is awaited (S1712).
In the wireless control unit on the receiving side, the DMA controller is set beforehand to a mode for transfer from the channel codec 208 to the memory 205. When data are received ("YES" at S1713), bit synchronization is established in the preamble section of the received data in the channel codec 208. When a unique word is detected, descrambling is performed. In addition, a DMA request is generated in units of one byte in the data section. Upon receiving the DMA request, the DMA controller transfers data from the channel codec 208 to the memory 205 (S1714). When transfer of one packet of data is finished, a reception-completion interrupt is generated by the channel codec 208 and the CPU applies error correction demodulating processing to the data stored in the memory 205. As a result, the final reception data are obtained and the data are transferred to the personal computer (S1715).
Transmission of data can be carried out through the procedure described above. In a case where there are data still to be transmitted, the same procedure is repeated by reason of the fact that execution of the application is unfinished ("NO" at S1716). This makes it possible to transmit an unlimited amount of data.
As shown in FIG. 10, the changeover of frequency of the control channel when data communication is being carried out in the manner described above is F1, F2, F3, F4, . . . , and the changeover of frequency of the data channel is F5, F6, F7, F8, . . . .
In other words, the changeover of frequency for data communication only (voice communication is not performed) is F1, F5, F2, F6, F3, F7, . . . , as shown in FIG. 19.
Other Forms of Communication
Described next will be a case where a request for data communication shown in FIGS. 16 and 17 is issued while voice communication illustrated in FIGS. 14 and 15 is in progress, i.e., a case where a file transfer is performed between a first personal computer and a second personal computer while voice communication is being carried out via a network controller using a handset connected to the first personal computer.
The hopping patterns used in simultaneous voice communication and data communication are decided individually just as at the time of voice communication and at the time of data communication. That is, both forms of communication are carried out using entirely different hopping patterns. The personal computer that performs voice communication and data communication simultaneously stores the first hopping pattern for the control channel, the second hopping pattern for the voice channel and the third hopping pattern for the data channel in the HP register 306 of the channel codec 208.
The wireless unit 209 performs communication by changing over frequency in accordance with the three hopping patterns that have been stored in the HP register 306 of the channel codec 208.
More specifically, as shown in FIG. 10, the wireless unit abides by the hopping pattern (F1, F2, F3, F4, . . . ) of the control channel, the hopping pattern (F3, F4, F5, F6, . . . ) of the voice channel and the hopping pattern (F5, F6, F7, F8, . . . ) of the data channel, and frequency is changed over in the manner F1, F3, F5, F2, F4, F6, F3, F5, F7, . . . , as depicted in FIG. 11.
Call Termination Control
A case where an incoming call is terminated at a wireless terminal will now be described.
FIG. 20 is a flowchart of the operation performed by the control station in a case where an incoming call from the public switched telephone network is terminated at the network control station, and FIG. 21 is a flowchart of operation performed by the wireless terminal in a case where an incoming call from the public switched telephone network is terminated at the network control station.
When an incoming call from the public switched telephone network is terminated at the network control station (at step S2001 in FIG. 20), the control station writes a call termination command to the LCCH register 310 of the channel codec 208, writes the address of the terminating wireless terminal to the destination address register 328, then sets the mode register 305 of the channel codec 208 to the LCCH transmission mode and notifies the terminating wireless terminal of the fact that there is an incoming call (S2002). The hopping pattern used in transmission of the LCCH data is the first hopping pattern, which is the same as that of the CNT channel.
The wireless terminal (a personal computer in this embodiment) that has received the termination command ("YES" at S2101) executes termination processing, such as issuance of an incoming call tone, to notify the user of the incoming call (S2102). When an answer corresponding to the incoming call is made by the user (S2103), the wireless terminal writes a termination answer command to the LCCH register 310 in the channel codec 208 in order to notify the control station of the fact that the incoming call has been answered, writes the address of the centralized control station to the destination address register, then sets the mode register 305 of the channel codec 208 to the LCCH transmission mode and notifies the centralized control station of the fact that the incoming call has been answered (S2104).
Upon receiving the termination answer command (S2003), the centralized control station notifies the answering personal computer of the hopping pattern used when data transmitted to the public telephone line or received from the public telephone line are exchanged between the personal computer and the centralized control station (S2004).
Here, with regard to the incoming call from the public telephone line, all data will be regarded as voice data and it will be assumed that the hopping pattern of which the personal computer is notified also is the second hopping pattern for the voice channel. The reason for this is that since all of the data sent from the public telephone line arrive upon being modulated as voice data, the data can be treated as voice data even if they are facsimile data or data from personal computer.
When notification of the hopping pattern used ends, the centralized control station makes a transition to the voice communication phase just as at the time of origination of the outgoing call (S2005).
If the termination answer command from the personal computer is not received at S2003, the control station judges that the personal computer is incapable of communicating and notifies the public telephone line of the fact that the personal computer is busy (S2006).
If the personal computer that has notified the centralized control station at S2104 that it has answered the incoming call has its hopping pattern allocated by the centralized control station ("YES" at S2105), the personal computer sets the hopping pattern number used by the voice communication channel and the channel used in the HP register 306 of the channel codec 208 and starts the operation of the ADPCM codec (S2106). The personal computer then undergoes a transition to the voice communication phase similar to that which prevailed when the outgoing call was originated.
If it is found at step S2105 that allocation of the hopping pattern has not been performed, then the personal computer transmits the termination answer command to the centralized control station again.
If the personal computer issues an origination request for data communication while it is performing communication in response to an incoming call from the public telephone line, the above-described origination control phase for data communication is carried out. Even if the personal computer is already performing data communication, it is capable of carrying out the above-described termination control phase if there is an incoming call.
Thus, as described above, communication using the control channel, the voice channel and the data channel is performed in accordance with hopping patterns that differ from one another. As a result, one wireless terminal can communicate simultaneously with a plurality of other wireless terminals having different hopping patterns.
Second Embodiment
A second embodiment of the present invention will now be described. The wireless communication system and wireless control unit of this embodiment have architectures identical with those of the wireless communication system and wireless control unit according to the first embodiment.
FIG. 22 is a block diagram showing the architecture of a channel codec in a system according to the second embodiment of the invention. The codec includes an address register 328 for storing the address which is the destination of communication. The other components of this codec are the same as those in the channel codec of the first embodiment illustrated in FIG. 3.
FIGS. 23A-23E are diagrams showing the structures of wireless frames used in the system according to the second embodiment. The basic components are the same as those of the wireless frames used in the system according to the first embodiment. The difference between the first and second embodiments in terms of the wireless frame elements is that each channel of the wireless frames according to the second embodiment has a system ID (ID) for receiving only data from the centralized control station that belongs to the same system. By thus providing an ID portion for each channel, it is possible to prevent the system from accidentally receiving data transmitted by another system.
The concept of frequency hopping used in the system according to this embodiment and the hopping patterns are the same as those used in the system according to the first embodiment.
The basic operation of the wireless control unit according to this embodiment will be described.
Since each channel of the wireless frames in this embodiment is provided with the ID portion, as mentioned above, the wireless control unit performs the operation, described below, using this ID.
In the LCCH channel shown in FIG. 23C, the CPU on the sending side uses the LCCH assembler/disassembler 314 to assemble the data that have been stored in the LCCH register 310 and the data in the ID register 308 within the channel codec 208. The assembled data are transmitted at the predetermined timing. On the receiving side, the received LCCH channel is disassembled by the LCCH assembler/disassembler 314. If and only if the received system ID matches the value that has been written in its own ID register 308, the receiving side stores the disassembled data in the LCCH register 310. Once this has been done, an interrupt is generated and applied to the CPU. In response to the interrupt, the CPU reads the data in the register.
With regard to the voice channel, the channel codec uses the voice assembler/disassembler 316 to assemble data that have entered via the ADPCM interface 304 and data in the ID register 308 and transmits the assembled data at the predetermined timing. Conversely, on the receiving side, the received voice channel is disassembled by the voice assembler/disassembler 316 at the predetermined timing and the results are outputted via the ADPCM interface 304, at the timing at which processing is performed in the ADPCM codec 207, only if the received system ID matches the value that has been stored in the receiving side's own ID register 308.
With regard to the data channel, the data are transmitted only if the CPU has requested data transmission. If data transmission has been requested, the CPU bus interface 303 of the channel codec 208 outputs a DMA request to the DMA controller (DMAC) 206 at the timing of every byte. When the DMAC 206 responds to the DMA request and data is written, the data is converted to a serial one by the data assembler/disassembler 315, the data is assembled together with the data in the ID register 308 and the resulting data are transmitted at the predetermined timing. Conversely, in a case where the data channel is received, the data assembler/disassembler 315 disassembles the data and, if the received system ID matches the value that has been written in the receiving side's own ID register 308, converts the data to parallel data. Operation from this point onward is the same as that of the first embodiment.
The operation of the system according to this embodiment will now be described. Here also it will be assumed that the network controller connected to the public telephone line functions as a centralized control station.
Voice Communication Control Operation
FIG. 24 is a flowchart showing a voice communication control operation according to this embodiment. Processing steps identical with those of the voice communication control operation according to the first embodiment shown in FIG. 14 are designated by like step numbers and need not be described again. Further, processing following transition to the voice communication phase is the same as illustrated in FIG. 15.
In a case where a carrier is not detected at step S1407 in FIG. 24, it may be considered that another terminal is not using the LCCH channel. Accordingly, in this embodiment, the data in the LCCH register 310, the address register 328 and the ID register 308 are read out, the frame of the logical control channel is assembled (S1108) and transmission of data to the centralized control station is started (S1409).
When the LCCH channel is received on the side of the personal computer by way of the first hopping pattern (S1110), the LCCH assembler/disassembler 314 in the channel codec 208 disassembles the received LCCH frame (S1111). The system ID sent in the system ID portion and the system ID in the ID register of the channel codec are compared and it is determined whether the address sent in the transmission-destination address portion matches the address on the side of the personal computer (S1112). If the result is that the system IDs match and the address is that of the terminal on the receiving side ("YES" at S1113), then the ensuing data are received. In other words, the notification of call termination, the hopping pattern and allocation of the channel used are received (S1410).
When bit synchronization is established in the preamble section of the received voice data in the voice channel, the unique word is detected and the system ID matches the system ID in the ID address register 308 at the time that audio is received, descrambling is carried out. The descrambled data are decoded by the ADPCM codec 207 and the decoded data are outputted as a voice from the speaker of the handset.
Data Communication Control Operation
FIGS. 25 and 26 are flowcharts showing a data communication control operation according to the second embodiment. Processing steps identical with those of the data communication control operation according to the first embodiment shown in FIGS. 16 and 17 are designated by like step numbers and need not be described again.
In a case where a carrier is not detected at step S1606 in FIG. 25, it may be considered that another terminal is not using the LCCH channel. Accordingly, the data in the LCCH register 310, the address register 328 and the ID register 308 are read out, the frame of the LCCH channel is assembled (S1308) and transmission of data to the centralized control station is started (S1608).
When the LCCH channel is received on the side of the personal computer by way of the first hopping pattern (S1310), the LCCH assembler/disassembler 314 in the channel codec 208 disassembles the received LCCH frame (S1311).
The system ID sent in the system ID portion and the system ID in the ID register of the channel codec are compared and it is determined whether the address sent in the transmission-destination address portion matches the address on the side of the personal computer (S1312). If the result is that the system IDs match and the address is that of the terminal on the receiving side ("YES" at S1313), then the ensuing data are received. In other words, the notification of call termination, the hopping pattern and allocation of the channel used are received (S1609).
When a transition is made to the data communication phase and a carrier is not detected at step S1705 in FIG. 26, then a DMA request is generated in one byte units in conformity with the timing of the data channel. Upon receiving the DMA request, the DMA controller transfers the data to the memory 205 of the channel codec 208 (S1707). The channel codec 208 adds the preamble, the unique word and the system ID in the ID register 308 onto the data, assembles the LCCH channel (S1408) and then scrambles the data and transmits the scrambled data (S1708).
If data are received ("YES" at S1713) after the mode register of the channel codec is set to the reception mode (S1712), the data assembler/disassembler disassembles the LCCH channel in the channel codec 208 (S1415). Bit synchronization is established in the preamble section, the unique word is detected and the system ID in the system ID portion is compared with the system ID in the ID register 308 (S1416). If the two system IDs match ("YES" at S1417), descrambling is carried out.
Operation in a case where data communication is requested during the time that voice communication is in progress is the same as that described in the first embodiment. However, when communication is carried out while changing over frequency in accordance with the three above-mentioned hopping patterns that have been stored in the HP register in the system according to this embodiment, the system ID in the ID register 308 is added on for every channel transmitted at the frequency to which the changeover has been made. Data are received on the receiving side only if the received system ID matches the system ID in the ID register.
Termination Control Operation
Call terminal control in the system according to this embodiment will now be described.
FIG. 27 is a flowchart illustrating the control procedure performed by the control station when an incoming call is terminated, and FIG. 28 is a flowchart illustrating the control procedure performed by the wireless terminal when an incoming call is terminated. Processing steps in FIGS. 27 and 28 identical with those of the control procedure shown in FIGS. 20 and 21 are designated by like step numbers and need not be described again.
When an incoming call from the public telephone line is terminated at the network control station (S2001) in FIG. 27, the control station writes a call termination command to the LCCH register 310 of the channel codec 208, writes the address of the terminating wireless terminal to the destination address register 328, then sets the mode register 305 of the channel codec 208 to the LCCH transmission mode. The control station reads the call termination command out of the LCCH register 310, reads the address of the terminating wireless terminal out of the address register 328, reads the system ID out of the ID register 308 and assembles the LCCH channel (S1702). The control station gives notification of the incoming call by transmitting the LCCH channel to the terminating wireless terminal (S2002).
The wireless terminal (a personal computer in this embodiment) that has received the above-mentioned LCCH channel (S1801 in FIG. 28) disassembles the LCCH channel by the LCCH assembler/disassembler 314 in the channel codec 208 (S1802) and compares the system ID in the system ID portion and the system ID in the ID register 308 (S1803). If the two system IDs match ("YES" at S1804), then the ensuing data are received and the personal computer executes termination processing, such as issuance of an incoming call tone, to notify the user of the incoming call (S2102). When an answer corresponding to the incoming call is made by the user ("Yes" at S2103), the personal computer writes a termination answer command to the LCCH register 310 in the channel codec 208 in order to notify the control station of the fact that the incoming call has been answered (S1807), writes the address of the centralized control station to the destination address register (S1808), then sets the mode register 305 of the channel codec 208 to the LCCH transmission mode (S1809). The personal computer reads the termination answer command out of the LCCH register 310, reads the address out of the address register 328, reads the system ID out of the ID register 308 and assembles the LCCH channel (S1810). By transmitting this channel, the personal computer notifies the centralized control station of the fact that the incoming call has been answered (S2104).
Upon receiving the LCCH channel ("YES" at S1704), the centralized control station disassembles the LCCH channel by the LCCH assembler/disassembler 314 in the channel codec 208 (S1705) and compares the system ID in the system ID portion and the system ID in the ID register 308 (S1706). If the two system IDs are found to match ("YES" at S1707), then the ensuing data are received, whereby the termination answer command is received ("YES" at S1708). In order to notify the answering personal computer of the hopping pattern used when data transmitted to the public telephone line or received from the public telephone line are exchanged between the personal computer and the centralized control station, the LCCH channel to which the system ID, etc. have been added on is assembled again (S1709) and this is transmitted to the personal computer (S2004).
When notification of the hopping pattern used ends, the centralized control station makes a transition to the voice communication phase just as at the time of origination of the outgoing call (S2005).
If the personal computer that has notified the centralized control station that it has answered the incoming call subsequently receives the LCCH channel ("YES" at step S1812 in FIG. 28), the LCCH channel is disassembled by the LCCH assembler/disassembler 314 in the channel codec 208 (S1813). The system ID in the system ID portion is then compared with the system ID in the ID register 308 (S1814). If these system IDs match ("YES" at step S1815), then the ensuing data are received.
When the hopping pattern used is allocated by the centralized control station in accordance with the data received ("YES" at S1816), the second hopping pattern used in the voice communication channel and the channel used are set in the HP register 306 of the channel codec 208 and operation of the ADPCM codec is started (S2106). The personal computer then undergoes a transition to the voice communication phase similar to that which prevailed when the outgoing call was originated (S2107).
If it is found at step S1816 that allocation of the hopping pattern has not been performed, then the program returns to step S2104 and the personal computer transmits the termination answer command to the centralized control station again.
Thus, as described above, the system ID is added onto the control channel, voice channel and data channel in which communication is performed at frequencies that differ from one another. Therefore, even if another system is performing communication at the same frequency, data will no longer be received accidentally.
Thus, it is possible to prevent the accidental reception of data from another system even in a frequency-hopping communication apparatus in which frequency is changed over in the middle of a communication frame.
As many apparently widely different embodiments of the present invention can be made without departing from the spirit and scope thereof, it is to be understood that the invention is not limited to the specific embodiments thereof except as defined in the appended claims. | A communication apparatus time-division multiplexes a plurality of items of information which include control information and at least one item of communication information, and allocates a plurality of hopping patters for each of the plurality of items of information. Frequency is changed over for each item of information in accordance with the plurality of hopping patterns, which have been stored for each communication, and communication is carried out using the frequency to which the changeover has been made. | 7 |
[0001] This application is a Divisional of co-pending U.S. application Ser. No. 10/556,145 filed on Aug. 21, 2006 and claims priority under 35 U.S.C. §120. U.S. application Ser. No. 10/556,145 is the national phase under 35 U.S.C. §371 of International Application No. PCT/CA2004/000697 filed May 7, 2004 in Canada.
BACKGROUND OF THE INVENTION
[0002] (a) Field of the Invention
[0003] The invention relates to novel regulators of plasminogen activation and their use for regulating cell migration and treating cancer. Furthermore, the present invention relates to novel pharmaceutical compositions form regulating cell migration and treating cancer.
[0004] (b) Description of the Prior Art
[0005] Melanotransferrin (p97) possesses a high level of homology (37-39%) with human serum transferrin, human lactoferrin and chicken transferrin. It is a glycosylated protein that reversibly binds iron and was first found at high levels in malignant melanoma cells. Two forms of p97 have been reported, one of which is bound to cell membranes by a glycosylphosphatidylinositol anchor while the other form is both soluble and actively secreted. The exact physiological role of either membrane-bound p97 or secreted p97 is largely unexplored.
[0006] In the early 1980s, p97 was found to be expressed in much larger amounts in neoplastic cells and fetal tissues than in normal tissues. More recently, it was reported that p97 mRNA is widespread in normal human tissues. p97 is also expressed in reactive microglia associated with amyloid plaques in Alzheimer's disease. Normal serum contains very low levels of p97, which were reported to increase by 5- to 6-fold in patients with Alzheimer's disease.
[0007] It was previously demonstrated that recombinant human melanotransferrin (p97) is transported at high rate into the brain using both an in vitro model of the blood brain barrier (BBB) and in situ mouse brain perfusion (Demeule M, et al., 2002 J Neurochem 83:924-933). It was also shown that p97 transcytosis might involve the low-density lipoprotein related protein (LRP). This receptor is also known to mediate the internalization of the urokinase:plasminogen activator inhibitor:urokinase receptor complex (uPA:PAI-1:uPAR). Briefly, single-chain proenzyme-uPA is activated upon binding to its cell surface receptor uPAR, which is a glycosylphosphatidylinositol (GPO-anchored membrane protein. After its activation, uPA (which catalyzes the conversion of plasminogen to plasmin) is quickly inhibited by the plasminogen activator inhibitor type-1 (PAI-1). The inactive uPA:PAI-1 complex binds to uPAR and then is rapidly internalized by LRP. The uPA:PAI-1 complex is degraded in lysosomes whereas the uPAR is recycled at the cell surface. Other LRP ligands include pro-uPA, PAI-1, receptor-associated protein (RAP) and a diverse spectrum of structurally unrelated proteins.
[0008] Heart disease has topped the list of killer diseases every year but one since 1900. (The exception was 1918, when an influenza epidemic killed more than 450,000 Americans.) Stroke is the third leading cause of death in the United States, following cancer. Much of the progress is due to the development of effective medicines to control blood pressure and cholesterol, according to officials of the National Heart, Lung and Blood Institute. But, experts warn, the war against heart disease and stroke is not yet won. Every 33 seconds, an American dies of either heart disease or stroke. Nearly 62 million Americans have one or more types of cardiovascular disease, and these diseases cost our society more than $350 billion a year.
[0009] Two strategies are presently used to restore the flow after thrombosis: 1) clot dissolution with administration of plasminogen activators and 2) clot permeation by surgical intervention. The tissue-type plasminogen activator (tPA) and its conventional substrate plasminogen, are key players involve in fibrinolysis. Currently, tPA is used as a stroke therapy, however, its associated adverse effects might limit its efficiency.
[0010] It would be highly desirable to be provided with novel regulators of plasminogen activation and their use for regulating cell migration and treating cancer.
[0011] It would also be highly desirable to be provided with novel pharmaceutical compositions form regulating cell migration and treating cancer.
[0012] It would be highly desirable to be provided with a new treatment for thrombo-embolic disorders such as venous or arterial thrombosis, thrombophlebitis, pulmonary and cerebral embolism, thrombotic microangiopathy and intravascular clotting. Some of these disorders will lead for example in heart and cerebral strokes.
[0013] It would be also desirable to be provided with a new method for increasing fibrinolysis or for preventing angiogenesis.
SUMMARY OF THE INVENTION
[0014] One aim of the present invention is to provide novel regulators of plasminogen activation and their use for regulating cell migration and treating cancer.
[0015] Another aim of the present invention is to provide novel pharmaceutical compositions form regulating cell migration and treating cancer.
[0016] A further aim of the present invention is to provide a new treatment for thromboembolic disorders such as, for example, without limitation, venous or arterial thrombosis, thrombophlebitis, pulmonary or cerebral embolism, thrombotic microangiopathy or intravascular clotting, some of which will lead for example in heart or cerebral strokes.
[0017] An additional aim of the present invention is to provide a new method for increasing fibrinolysis or for preventing angiogenesis.
[0018] In accordance with one embodiment of the present invention there is provided a method for increasing plasminogen activation, said method comprising contacting a solution containing pro-uroquinase plasminogen activator (pro-uPA) with melanotransferrin (p97) or an enzymatically active fragment thereof for a time sufficient to increase plasminogen activation.
[0019] In a preferred embodiment, p97 increase plasminogen activation and fibrinolysis through tissue plasminogen activator (t-PA).
[0020] In accordance with another embodiment of the present invention there is provided a method for inhibiting plasminogen activation, said method comprising the step of contacting pro-uroquinase plasminogen activator (pro-uPA) with membrane bound melanotransferrin (p97) for a time sufficient to prevent plasminogen activation.
[0021] In accordance with a further embodiment of the invention, there is provided a method for preventing cell migration, said method comprising the step of contacting a cell expressing melanotransferrin (p97) on its surface with exogenous soluble 97 or an antibody, or an antigen binding fragment thereof, directed to said p97 expressed on the surface of said cell, said soluble p97 competing with the p97 expressed on the cell surface, activating plasminogen in solution instead of membrane-bound plasminogen, thus preventing cell migration, said antibody, or active fragment thereof binding p97 on the surface of the cell thus preventing activation of membrane-bound plasminogen, preventing cell migration.
[0022] In a preferred embodiment of the invention, the antibody is a monoclonal antibody, and more preferably one of L235, HybC, HybE, HybF, 9B6 or 2C7.
[0023] The cell can be for example, without limitation, an endothelial cell or a tumor cell, such as one selected from the group consisting of human vascular or microvascular endothelial cells such as HMEC-1 and human melanoma cells such as SK-MEL28 cells.
[0024] Still in accordance with the present invention, there is provided a method for treating cancer caused by cells expressing melanotransferrin (p97) at their surface, said method comprising the step of administering to a patient in need thereof exogenous soluble p97 or an antibody an antibody, or active fragment thereof, directed to said p97 expressed on the surface of said cell, said soluble p97 competing with the p97 expressed on the cell surface, activating plasminogen in solution instead of membrane-bound plasminogen, thus preventing cell migration, said antibody, or active fragment thereof binding p97 on the surface of the cell thus preventing activation of membrane-bound plasminogen, preventing cell migration, preventing cancer cells from spreading.
[0025] Further in accordance with the present invention, there is provided a method for regulating capillary tube formation, said method comprising the step administering to a patient in need thereof soluble 97, wherein said soluble p97 prevents or reduces capillary tube formation.
[0026] Also in accordance with the present invention, there is provided a pharmaceutical composition for use in regulating activation of plasminogen, said composition comprising a therapeutically effective amount of melanotransferrin (p97) or an enzymatically active fragment thereof in association with a pharmaceutically acceptable carrier.
[0027] Preferably, p97 is soluble p97 for increasing activation of plasminogen.
[0028] In accordance with the present invention there is also provided a method of regulating the activation of plasminogen, comprising administering to an individual in need thereof a therapeutically effective amount of the aforementioned pharmaceutical composition.
[0029] In accordance with the present invention there is also provided a pharmaceutical composition for use in regulating cell migration of a cell showing p97 activity, comprising a therapeutically effective amount of one of p97, an enzymatically active fragment thereof, or an antibody recognizing specifically p97, or an antigen binding fragment thereof, in association with a pharmaceutically acceptable carrier.
[0030] Further in accordance with the present invention there is also provided a method of regulating cell migration of a cell showing p97 activity, comprising administering to an individual in need thereof a therapeutically effective amount of the aforementioned pharmaceutical composition.
[0031] In accordance with the present invention there is further provided a pharmaceutical composition for treating cancer comprising a therapeutically effective amount of one of melanotransferrin (p97), an enzymatically active fragment thereof, or an antibody recognizing specifically p97, or an antigen binding fragment thereof, in association with a pharmaceutically acceptable carrier.
[0032] Also in accordance with the present invention there is further provided a method of treating cancer, comprising administering to an individual a therapeutically effective amount of the aforementioned pharmaceutical composition.
[0033] The cancer can be, for example, without limitation, selected from the group consisting of melanoma, prostate cancer, leukemia, hormone dependent cancer, breast cancer, colon cancer, lung cancer, skin cancer, ovarian cancer, pancreatic cancer, bone cancer, liver cancer, biliary cancer, urinary organ cancer (for example, bladder, testis), lymphoma, retinoblastoma, sarcoma, epidermal cancer, liver cancer, esophageal cancer, stomach cancer, cancer of the brain and cancer of the kidney.
[0034] In accordance with the present invention there is also provided a pharmaceutical composition for use in regulating angiogenesis comprising a therapeutically effective amount of melanotransferrin (p97) or an enzymatically active fragment thereof in association with a pharmaceutically acceptable carrier.
[0035] Still in accordance with the present invention there is also provided a method of regulating angiogenesis, comprising administering to an individual a pharmaceutically effective amount of the aforementioned pharmaceutical composition.
[0036] In accordance with the present invention, there is provided the use of p97, or an enzymatically active fragment thereof, or of any of the aforementioned composition for the various uses described herein or for the manufacture of medication for the various use described herein.
[0037] For the purpose of the present invention the following terms are defined below.
[0038] The term “p97” is also referred to in the present invention as Melanotransferrin, MTf, or P97. All of these terms are being used interchangeably. The term soluble p97 thus make reference to soluble p97 or soluble melanotransferrin.
[0039] The term “cancer” is intended to mean any cellular malignancy whose unique trait is the loss of normal controls which results in unregulated growth, lack of differentiation and ability to invade local tissues and metastasize. Cancer can develop in any tissue of any organ. More specifically, cancer is intended to include, without limitation, melanoma, prostate cancer, leukemia, hormone dependent cancers, breast cancer, colon cancer, lung cancer, skin cancer, ovarian cancer, pancreatic cancer, bone cancer, liver cancer, biliary cancer, urinary organ cancers (for example, bladder, testis), lymphomas, retinoblastomas, sarcomas, epidermal cancer, liver cancer, esophageal cancer, stomach cancer, cancer of the brain and cancer of the kidney. Cancer is also intended to include, without limitation, metastasis, whether cerebral, pulmonary or bone metastasis, from various types of cancers, such as melanomas, or from any types of cancer mentioned above.
[0040] The terms “treatment”, “treating” and the like are intended to mean obtaining a desired pharmacologic and/or physiologic effect, e.g., inhibition of cancer cell growth. The effect may be prophylactic in terms of completely or partially preventing a disease or symptom thereof and/or may be therapeutic in terms of a partial or complete cure for a disease and/or adverse effect attributable to the disease. “Treatment” as used herein covers any treatment of a disease in a mammal, particularly a human, and includes: (a) inhibiting the disease, (e.g., arresting its development); or (B) relieving the disease (e.g., reducing symptoms associated with the disease).
[0041] The term “administering” and “administration” is intended to mean a mode of delivery including, without limitation, oral, rectal, parenteral, subcutaneous, intravenous, intramuscular, intraperitoneal, intraarterial, transdermally or via a mucus membrane. The preferred one being orally. One skilled in the art recognizes that suitable forms of oral formulation include, but are not limited to, a tablet, a pill, a capsule, a lozenge, a powder, a sustained release tablet, a liquid, a liquid suspension, a gel, a syrup, a slurry, a suspension, and the like. For example, a daily dosage can be divided into one, two or more doses in a suitable form to be administered at one, two or more times throughout a time period.
[0042] The term “therapeutically effective” is intended to mean an amount of a compound sufficient to substantially improve some symptom associated with a disease or a medical condition. For example, in the treatment of cancer, a compound which decreases, prevents, delays, suppresses, or arrests any symptom of the disease would be therapeutically effective. A therapeutically effective amount of a compound is not required to cure a disease but will provide a treatment for a disease such that the onset of the disease is delayed, hindered, or prevented, or the disease symptoms are ameliorated, or the term of the disease is changed or, for example, is less severe or recovery is accelerated in an individual.
[0043] The compounds of the present invention may be used in combination with either conventional methods of treatment and/or therapy or may be used separately from conventional methods of treatment and/or therapy.
[0044] When the compounds of this invention are administered in combination therapies with other agents, they may be administered sequentially or concurrently to an individual. Alternatively, pharmaceutical compositions according to the present invention may be comprised of a combination of a compound of the present invention, as described herein, and another therapeutic or prophylactic agent known in the art.
[0045] It will be understood that a specific “effective amount” for any particular individual will depend upon a variety of factors including the activity of the specific compound employed, the age, body weight, general health, sex, and/or diet of the individual, time of administration, route of administration, rate of excretion, drug combination and the severity of the particular disease undergoing prevention or therapy.
[0046] Pharmaceutically acceptable acid addition salts may be prepared from inorganic and organic acids. Salts derived from inorganic acids include hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and the like. Salts derived from organic acids include citric acid, lactic acid, tartaric acid, fatty acids, and the like.
[0047] As used herein, “pharmaceutically acceptable carrier” includes any and all solvents (such as phosphate buffered saline buffers, water, saline), dispersion media, coatings, antibacterial and antifungal agents, isotonic and absorption delaying agents and the like. The use of such media and agents for pharmaceutically active substances is well known in the art. Except insofar as any conventional media or agent is incompatible with the active ingredient, its use in therapeutic compositions is contemplated. Supplementary active ingredients can also be incorporated into the compositions.
BRIEF DESCRIPTION OF THE DRAWINGS
[0048] FIG. 1A-1B illustrates that ( 1 A) a significant (>50%) reduction in the transport of [125I]-p97 (25 nM) from the apical (blood side) to the basolateral side (brain side) of bovine brain capillary endothelial cell (BBCEC) monolayers is observed in the presence of 640 nM receptor-associated protein (RAP) and that ( 1 B) no interactions are observed between RAP and BSA proteins and p97, suggesting that the inhibition of [ 125 I]-p97 transcytosis is not related to protein interactions between p97 and RAP;
[0049] FIG. 2 illustrates that various monoclonal antibodies to p97 are still able to recognize p97 following their immobilization to a sensor chip surface, indicating that the p97 protein remains intact following immobilization;
[0050] FIG. 3A-3B illustrates that ( 3 A) sensor chip surface immobilized p97 can interact with pro-uPA but no interaction can be detected between p97 and PAI-1 or between p97 and tPA and that ( 3 B) plasminogen also interacts with immobilized p97 whereas plasmin and angiostatin, two plasminogen fragments do not;
[0051] FIG. 4 illustrates the effects of p97 on pro-uPA, tPA and plasminogen and shows that (A) VLK-pNA hydrolysis by pro-uPA increases when p97 is added to the reaction; (B) p97 elicits no observable effect on tPA; (C) the interaction of p97 with pro-uPA does not result in the cleavage of either protein; and (D) p97 alters the cleavage of glu-plasminogen by pro-uPA;
[0052] FIG. 5 illustrates plasminogen activation by p97 and shows that (A) VLK-pNA hydrolysis is 4-fold higher when p97 is added to pro-uPA and plasminogen; (B) p97 stimulates plasminogen cleavage by pro-uPA in a dose-dependent manner; (C) p97 positively affects the activation of plasminogen by pro-uPA by increasing the catalytic efficiency of pro-uPA; and (D) the effect of p97 upon pro-uPA's activation of plasminogen is specific and involves the epitope recognized by the mAb L235;
[0053] FIG. 6 illustrates the inhibition of cell migration by mAb L235, an antibody to p97, and shows that (A) the presence of mAb L235, inhibits the migration of HMEC-1 and SK-MEL28 cells but not HUVEC cells; and (B) p97 is highly expressed in lysates from HMEC-1 and SK-MEL29 cells and at lower levels in their respective conditioned culture media, but is almost undetectable in HUVEC cells;
[0054] FIG. 7 illustrates that (A) exogenous p97 inhibits the migration of MHEC-1 cells and (B) SK-MEL28 cells; and (C) the level of inhibition is 50% and 70%, respectively at 100 nM p97 for those same cells respectively;
[0055] FIG. 8 illustrates the inhibition of plasminolytic activity at the cell surface by soluble p97 and mAb L235 and shows that (A) 100 nM p97 results in 95% inhibition of plasminogen activation in HMEC-1 cells; and (B) mAb L235 results in more than 50% inhibition of plasminolytic activity;
[0056] FIG. 9 illustrates the stimulatory effect of p97 on plasminogenolytic activity of single chain urokinase plasminogen activator (sc-uPA), uPA and tissue plasminogen activator (tPA) in vitro;
[0057] FIG. 10 illustrates that low density lipoprotein related protein (LRP) and the urokinase activator receptor (uPAR) are down regulated in p97 treated HMEC-1 cells;
[0058] FIG. 11 illustrates that soluble p97 inhibits the morphogenic differentiation of HMEC-1 ( 11 A) and HUVEC ( 11 B) into capillary-like structures, when grown onto Matrigel-coated wells in the presence or absence of soluble p97 (10 nM or 100 nM) as described in the Materials and Methods sections hereinafter, the length of the total capillary network being quantified after 18 hours using a map scale calculator by measuring and summing the length of all tubular structures observed in a chosen field. The results were expressed as the percentage of capillary-like tubes in soluble p97-treated cells compared to untreated HMEC-1 and HUVEC cells ( 11 C);
[0059] FIG. 12 illustrates that soluble p97 inhibits HMEC-1 cell migration ( 12 A and 12 B) without affecting cell adhesion ( 12 C);
[0060] FIG. 13 illustrates that soluble p97 down-regulates u-PAR ( 13 A) and LRP protein ( 13 B) expression;
[0061] FIG. 14 illustrates that soluble p97 unaffects the u-PAR/LRP system mRNA expression;
[0062] FIG. 15 illustrates that soluble p97 modulates the cell surface levels of u-PAR ( 15 A) and LRP ( 15 B) and binding of 125I-uPA•PAI-1 ( 15 C) complex on the HMEC-1 cell surface;
[0063] FIG. 16 illustrates that soluble p97 up-regulates Cav-1 and down-regulates pERK 1/2 ( 16 D) protein expression and wherein the level in control cells ( 16 B) and ERK 1/2 ( 16 C) was unchanged;
[0064] FIG. 17 illustrates that soluble p97 down-regulates eNOS protein expression ( 17 A) as well as VEGFR-2 and VEGF-A mRNA levels ( 17 B);
[0065] FIG. 18 is a schematic representation of soluble p97 treatment effects on the u-PAR/LRP system;
[0066] FIG. 19 illustrates that soluble p97 enhance cell detachment ( 19 A), plasminolytic activity ( 19 B) and plasmin formation in HEMEC-1 ( 19 C);
[0067] FIG. 20 illustrates inhibition of cell detachment ( 20 A) and plasmin formation ( 20 B) by inhibitors;
[0068] FIG. 21 illustrates that cell detachment stimulated by soluble p97 induces degradation of fibronectin in HMEC-1;
[0069] FIG. 22 illustrates the interaction between p97 and plasminogen using biospecific interaction analysis in real-time;
[0070] FIG. 23 illustrates the effects of p97 interaction with plasminogen (Plg) on tPA-dependant plasmin activity, and more specifically demonstrates that the presence of p97 increases the plasminogen activation ( 23 A), that the induction caused by p97 of the plasminogen activity is inhibited by the monoclonal antibody directed against p97 ( 23 B), the plasminolytic activity of tPA in the presence of p97 ( 23 C), and that soluble p97 decreases the apparent K m of tPA for plasminogen ( 23 D);
[0071] FIG. 24 illustrates fibrin clot permeation in the presence of p97 ( 24 A), the size increase of the perforation as a function of soluble p97 concentration ( 24 B), and the intrinsic fibrinolytic activity of soluble p97 ( 24 C);
[0072] FIG. 25 illustrates the effects of p97 on plasma clot fibrinolysis by tPA;
[0073] FIG. 26 illustrates the effect of p97 on clot strength and fibrinolysis, and more specifically of a thromboelastogram of a fibrin clot model ( 26 A) and of a plasma recalcified after addition of 2 nM CaCl 2 ( 26 B);
[0074] FIG. 27 illustrates that L235 ( 27 A) and soluble p97 ( 27 B) inhibited membrane bound p97-induced CHO cell invasion.
[0075] FIG. 28 illustrates transendothelial invasion across the blood-brain barrier of CHO cells transfected with (mMTf-CHO cells) or without (Mock-CHO cells) membrane bound p97; and
[0076] FIG. 29 illustrates that ( 29 A) the interaction of pro-uPA and plasminogen with soluble p97 increases the activation of plasminogen; this induction can be inhibited by the mAb L235 which recognizes a conformational epitope on p97; ( 29 B) the addition of mAb L235 reduces the plasminolytic activity on HMEC-1 cell surfaces and results in an inhibition of cell migration and ( 29 C) the interaction of plasminogen and pro-uPA with membrane-bound p97 is diminished when exogenous, competing human recombinant p97 is added, which also results in a decrease in the activation of plasminogen and leads to an inhibition of cell migration.
DETAILED DESCRIPTION OF THE INVENTION
Materials and Methods
[0077] Soluble human recombinant p97 which is produced by introducing a stop codon following the glycine residue at position #711 (of SEQ ID NO:1) and monoclonal antibodies (mAbs) directed against p97 were kindly provided by Biomarin Pharmaceutical Inc. (Novato, Calif.). TPA, PAI-1 and plasmin are from Calbiochem (La Jolla, Calif.). Pro-uPA and plasminogen are from American Diagnostica (Greenwich, Conn.). Angiostatin is purchased from Angiogenesis Laboratories (Tucson, Ariz.) whereas uPA is from Roche Biochemicals (Laval, QC). CM5 sensor chips are from BIAcore (Piscataway, N.J.). The plasmin substrate (D-val-leu-lys-p-nitraniline or VLK-pNA) and other biochemical reagents are from Sigma (Oakville, ON).
[0078] Antibodies directed against α-LRP (8G1 clone) and u-PAR (#3937) were from Research Diagnostics Inc. (Flanders, N.J.) and American Diagnostica (Greenwich, Conn.), respectively. Antibodies directed against Cav-1 (#C3721) and phosphorylated Cav-1 (pCav-1) (#61438) were from BD Transduction Laboratories (Lexington, Ky.). The antibody directed against eNOS (#N30020) was from BD Biosciences (Mississauga, ON) and the antibody directed against GAPDH (#RGM2) was from Advanced Immunochemical Inc. (Long Beach, Calif.). Antibodies directed against extracellular signal-regulated kinase 1/2 (ERK 1/2) (#9102) and pERK 1/2 (#9101S) were from Cell Signaling Technology (Beverly, Mass.). Other biochemical reagents were from Sigma (Oakville, ON).
Blood-Brain Barrier Model and Transcytosis Experiments
[0079] The in vitro model of the blood-brain barrier (BBB) is established by using a co-culture of bovine brain capillary endothelial cells (BBCEC) and newborn rat astrocytes as previously mentioned (Demeule et al., Journal of Neurochemistry, 83: 924-933, 2002). p97 is radioiodinated with standard procedures using an iodo-beads kit and D-Salt Dextran desalting columns from Pierce, as previously described (Demeule M, et al., 2002 J Neurochem 83:924-933). Transcytosis experiments are performed as follows: one insert covered with BBCECs is set into a six-well microplate with 2 ml of Ringer-Hepes and is pre-incubated for 2 h at 37° C. [ 125 I]-p97 (0.5-1.5 μCi/assay), at a final concentration of 25 nM, is then added to the upper side of the insert. At various times, the insert is sequentially transferred into a fresh well to avoid possible reendocytosis of p97 by the abluminal side of the BBCECs. At the end of the experiment, [ 125 I]-p97 is assayed in 500 μl of the lower chamber of each well following TCA precipitation.
Cell Culture
[0080] Cells are cultured under 5% CO 2 /95% air atmosphere. Human microvascular endothelial cells (HMEC-1) are from the Center for Disease Control and Prevention (Atlanta, Ga.) and are cultured in MCDB 131 media (Sigma) supplemented with 10 mM L-glutamine, 10 ng/ml epidermal growth factor (EGF), 1 μg/ml hydrocortisone and 10% inactivated foetal bovine serum (FBS). Human umbilical vein endothelial cells (HUVEC) and SK-MEL28 are obtained from ATCC (Manassas, Va.). HUVECs are cultured in EGM-2 medium (bullet kit, Clonetics #CC-3162) and supplemented with 20% FBS. Melanoma SK-MEL28 cells are grown in MEM supplemented with 1 mM Na-pyruvate, 100 U/ml penicillin-streptomycin, 1.5 g/L Na-bicarbonate and 10% FBS.
BIAcore Analysis
[0081] p97, PAI-1 and plasminogen are covalently coupled to a CM5 sensor chip via primary amine groups using the N-hydroxysuccinimide (NHS)/N-ethyl-N′-(dimethylaminopropyl)carbodiimide (EDC) coupling agents. Briefly, the carboxymethylated dextran is first activated with 50 μl of NHS/EDC (50 mM/200 mM) at a flow rate of 5 μl/min. p97, PAI-1 or plasminogen (5 μg) in 20 mM acetate buffer, pH 4.0 are then injected and the unreacted NHS-esters are deactivated with 35 μl of 1 M ethanolamine hydrochloride, pH 8.5. Approximately 8000 to 10000 relative units of p97, PAI-1 or plasminogen are immobilized on the sensor chip surface. Ringer solution or a 50 mM Tris/HCl buffer (pH 7.5) containing 150 mM NaCl and 50 mM CaCl 2 is used as the eluent buffer. Proteins are diluted in the corresponding eluent buffer and injected onto the sensor chip surface. Protein interactions are analyzed using both the Langmuir binding model, which is the simplest model for 1:1 interaction between analyte and immobilized ligand, and a two-state conformational change model which describes a 1:1 binding of analyte to immobilized ligand followed by a conformational change.
[0000] Enzymatic Assay and Cell Treatment with Soluble p97
[0082] The enzymatic activity of pro-uPA is measured using a colorimetric assay. The reaction is performed in a final volume of 200 μl in an incubation medium consisting of 50 mM Tris/HCl buffer (pH 7.5), 150 mM NaCl, and 50 mM CaCl 2 . This incubation medium also contains 15 μg/ml VLK-pNA with or without plasminogen. Enzymatic activity is assessed in the absence or presence of p97. The reaction is started by the addition of pro-uPA. In this assay, the cleavage of VLK-pNA results in a p-nitraniline molecule that absorbs at 405 nm. The reaction product is monitored at 405 nm using a Microplate Thermomax Autoreader (Molecular Devices, CA).
[0083] HMEC-1 are grown to 85% confluency in 6-well plates and are incubated 18 hrs under 5% CO 2 /95% air atmosphere in cell culture medium with or without p97 (100 nM). Endothelial cells are washed twice with Ringer solution and mechanically scraped from the wells. Cells are counted and frozen at −80° C. until used. A volume corresponding to 100,000 cells is incubated in the plasmin assay as above and plasmin activity is monitored at 405 nm for 60 min. HMEC-1 are also individualized by PBS citrate solution (138 mM NaCl, 2.7 mM KCl, 1.47 mM KH 2 PO 4 , 8.1 mM Na 2 HPO 4 -7H 2 O, 15 mM Na citrate pH 6.8) for 15 min. Cells are washed twice in Ringer-Hepes solution (150 nM NaCl, 5.2 mM KCl, 2.2 mM CaCl 2 , 0.2 mM MgCl 2 -6H 2 O, 6 mM NaHCO 3 , 5 mM Hepes, 2.8 mM Glucose, pH 7.4) and counted. A volume corresponding to 100,000 cells is incubated in the plasmin assay with mAb L235 (325 nM) or IgG control. Plasmin activity is monitored at 405 nm for 480 min.
Cell Migration Assay
[0084] HMEC-1, HUVEC and SK-MEL28 cell migration is performed using Transwell filters (Costar; 8 μm pore size) precoated with 0.15% gelatin for 2 hrs at 37° C. The transwells are assembled in 24-well plates (Falcon 3097) and the lower chambers filled with 500 μl of cell culture medium. To study the effect of p97, mAb L235 or mouse IgG on cell migration, HMEC-1, HUVEC and SK-MEL28 cells are harvested by trypsinization and centrifuged. Approximatively 10,000 cells are resuspended in 100 μl fresh DMEM medium with or without p97 (native or boiled for 30 minutes at 100° C.), mAb L235 or mouse IgG and added into the upper chamber of each transwell (lower chamber of the transwell also contains p97, mAb L235 or non-specific mouse IgG). The plates are then placed at 37° C. in 5% CO 2 /95% air for 18 hrs. Cells that had migrated to the lower surface of the filters are fixed with 3.7% formaldehyde in PBS (Ca 2+ /Mg 2+ free), stained with 0.1% crystal violet/20% MeOH, and counted (4 random fields per filter). Photomicrographs at 100× magnification are taken using a Polaroid Microcam or Nikon Coolpix™ 500 digital camera attached to a Nikon TMS-F microscope.
Cell Adhesion Assay
[0085] HMEC-1 cell adhesion was performed using 96-well plate precoated with 0.15% gelatin for 2 hrs at 37° C. To study the effect of soluble p97 on cell adhesion, HMEC-1 cells were harvested by trypsinization. 1×10 4 cells were resuspended in 100 μL of fresh medium with or without soluble p97 and added into each well. Cells were then incubated for 2 hrs at 37° C. After incubation, adherent cells were washed twice in PBS (Ca +2 /Mg +2 free) and stained with 0.1% crystal violet/20% MeOH. Then, cells were lysed in 1% sodium dodecyl sulfate (SDS) and cell lysates were measured at 595 nm using a Microplate Thermomax Autoreader™ (Molecular Devices, Sunnyvale, Calif.). After cell staining, adherent cells were visualized at a 100× magnification using a digital Nikon Coolpix™ 5000 camera attached to a Nikon TMS-F microscope.
Capillary Tube Formation on Matrigel
[0086] Matrigel (BD Bioscience, Mississauga, ON) was thawed on ice and 50 μL were added to a 96-well plate and incubated for 10 min at 37 C. HMEC-1 or HUVEC cells were harvested by trypsinization. 2.5×10 4 cells were resuspended in 100 μL fresh medium and added to Matrigel-coated wells for 30 min at 37 C. After cell adhesion, the medium was removed and 100 μL of fresh cell culture medium with or without soluble p97 was added. Cells were then incubated for 18 hrs at 37° C. After incubation, tubular structures were visualized at a 40× magnification using a digital Nikon Coolpix™ 5000 camera attached to a Nikon TMS-F microscope. The length of the total capillary network was quantified using a map scale calculator by measuring and summing the length of all tubular structures observed in a chosen field.
Western Blot Analysis
[0087] HMEC-1 (3×10 6 cells) were plated into a 75 cm 2 culture flask and exposed to complete medium containing 0, 10 or 100 nM soluble p97. After 18 hours treatment, the cells were washed twice with PBS (Ca +2 /Mg +2 free) and solubilized in lysis buffer (1% Triton-X-100™, 0.5% NP-40, 150 mM NaCl, 1 mM ethylenediaminetetraacetic acid (EDTA), 10 mM Tris, 2% N-octylglucoside, 1 mM orthovanadate, pH 7,5) for 30 minutes on ice. Supernatant proteins were measured using a micro-BCA (bicinchoninic acid) kit from Pierce (Rockford, Ill.). Conditioned media and cell lysates of HMEC-1 were subjected to SDS-polyacrylamide gel electrophoresis (SDS-PAGE), using 5% acrylamide gels for the detection of LRP α-subunit, 10% acrylamide gels for the detection of u-PAR and eNOS, 12% acrylamide gels for the detection of GAPDH, Cav-1, pCav-1, ERK 1/2 and pERK 1/2. Separated proteins were transferred from polyacrylamide gels to polyvinylidene difluoride membranes (PerkinElmer Life Sciences, Boston, Mass.) using a Minitrans-Blot™ cell from Bio-Rad (Mississauga, ON) for 90 minutes at 80 mA per gel. Following transfer, Western blot analysis was performed. All immunodectection steps were carried out in Tris-buffered saline/0.3% Tween, pH 8.0 (TBS-Tw (0.3%)). The primary antibody was diluted 1:250 for u-PAR, α-LRP, GAPDH; 1:1000 for eNOS; 1:5000 for Cav-1, pCav-1, ERK 1/2 and pERK 1/2. The secondary antibody, used for u-PAR, α-LRP, GAPDH, Cav-1, pCav-1 and eNOS immunodetection, was a horseradish peroxidase-conjugated anti-mouse IgG from Jackson Immunoresearch Laboratories (West Grove, Pa.) diluted 1:2500 in 5% powdered skimmed milk in TBS-Tw (0.3%). Whereas, the secondary antibody, used for ERK 1/2 and pERK 1/2 immunodetection, was a horseradish peroxidase-conjugated anti-rabbit IgG from Jackson Immunoresearch Laboratories diluted 1:2500 in 5% powdered skimmed milk in TBS-Tw (0.3%). Incubation with enhanced luminol reagent (PerkinElmer Life Sciences, Boston, Mass.) and exposure to x-ray film was used for protein detection. Protein levels were quantified by laser densitometry using Chemilmager™ 5500 from Alpha Innotech Corporation (San Leandro, Calif.). In addition, fibronectin and plasminogen were immunodetected by Western blot analysis in the cell media following HMEC-1 detachment.
Total RNA Isolation and Reverse Transcription Polymerase Chain Reaction (RT-PCR)
[0088] Total RNA was extracted from cultured HMEC-1 using TRIzol™ reagent from Invitrogen (Burlington, ON). RT-PCR reactions were performed using SuperScript™ One-Step RT-PCR with Platinum® Taq Kit from Invitrogen (Burlington, ON). RT-PCR reactions were performed using specific oligonucleotide primers, derived from human cDNA sequences for the low-density lipoprotein receptor (LDL-R) gene family (that includes LDL-R, LRP, LRP 1B, LRP 2, LRP 8), u-PAR, VEGFR-2, VEGF-A and GAPDH (see Table 1 for primer sequences). Gene product amplification was performed for 40 cycles of PCR (94° C. for 15 sec, 60° C. for 30 sec (55° C. for LRP 2), 72° C. for 1 min.). RT-PCR conditions have been optimized so that the gene products were at the exponential phase of amplification. Amplification products were fractionated on 2% (w/v) agarose gels and visualized by ethidium bromide.
[0000] TABLE 1 Polymerase chain reaction (PCR) primer sequences and estimated product sizes for u-PAR,LDL-R family gene, GAPDH, VEGFR-2 and VEGF-A. Product size Gene Primer sequences (bp) LRP S 5′-AGAAGTAGCAGGACCAGAGGG-3′ (SEQ ID NO: 2) 301 AS 5′-TCAGTACCCAGGCAGTTATGC-3′ (SEQ ID NO: 3) LRP 1B S 5′-TCTCTCCCTTCTCCAAAGACCC-3′ (SEQ ID NO: 4) 403 AS 5′-TCAATGAGTCCAGCCAGTCAGC-3′ (SEQ ID NO: 5) LRP 2 S 5′-CGGAGCAGTGTGGCTTATTTTC-3′ (SEQ ID NO: 6) 280 AS 5′-CAGGTGTATTGGGTGTCAAGGC-3 (SEQ ID NO: 7) LDL-R S 5′-GGACCCAACAAGTTCAAGTGTCAC-3′ (SEQ ID NO: 8) 377 AS 5′-AAGAAGAGGTAGGCGATGGAGC-3′ (SEQ ID NO: 9) LRP 8 S 5′-CCTTGAAGATGATGGACTACCCTCG-3′ (SEQ ID NO: 10) 415 AS 5′-AAAACCCAAAAAAGCCCCCCCAGC-3′ (SEQ ID NO: 11) u-PAR S 5′-ACCGAGGTTGTGTGTGGGTTAGAC-3′ (SEQ ID NO: 12) 306 AS 5′-CAGGAAGTGGAAGGTGTCGTTG-3′ (SEQ ID NO: 13) GAPDH S 5′-CCATCACCATCTTCCAGGAG-3′ (SEQ ID NO: 14) 540 AS 5′-CCTGCTTCACCACCTTCTTG-3′ (SEQ ID NO: 15) VEGFR- S 5′-AAAGACATTGCGTGGTCAGGCAGC-3′ (SEQ ID NO: 16) 521 2 AS 5′-GGCATCATAAGGCAGTCGTTCAC-3′ (SEQ ID NO: 17) 466 VEGF-A S 5′-CCAGCACATAGGAGAGATGAGCTT-3′ (SEQ ID NO: 18) 394 AS 5′-GGTGTGGTGGTGACATGGTTAATC-3′ (SEQ ID NO: 19) 262 S = sense strand; AS = antisense strand.
Binding of 125 I-uPA•PAI-1 Complexe to HMEC-1 Soluble p97-Treated Cells
[0089] First, u-PA was radioiodinated using standard procedures with Na- 125 I (Amersham Pharmacia Biotech, Baie D'Urfé, QC) and an iodo-beads kit from Pierce (Rockford, Ill.). 125 I-uPA•PAI-1 complexe was formed by incubating PAI-1 (277 nM) with two-chain 125 I-uPA (277 nM) at a molar ration of 1:1 for 1 hour at 37° C. HMEC-1 (6×10 5 cells) were plated onto multiwell (6 wells/plate) disposable plastic tissue culture plate using fresh media. When confluence was reach, the medium was removed and completed cell culture medium with or without soluble p97 (100 nM) was added for 18 hours. Binding experiments were performed at 4° C. to limit possible concomitant internalization during the binding interval. Briefly, after cell treatment, cell monolayers were washed and the binding was initiated by adding 10 nM of 125 I-uPA•PAI-1 complexe in 1 mL of Ringer/HEPES containing 0.05% ovalbumine. After 1 hour incubation, cells were washed three times and lysed with 1 mL NaOH (0.3 M). Cell associated radioactivity was quantitated in 800 μL after trichloroacetic acid (TCA) precipitation. The protein content of control and soluble p97-treated HMEC-1 cells was measured by using Coomassie® Plus Protein Assay Reagent kit (Pierce, Rockford, Ill.).
[0000] Fluorescence-Activated Cell Sorting (FACS) Analysis of Cell Surface u-PAR
[0090] HMEC-1 (3×10 6 cells) were plated onto 75 cm 2 dishes using fresh media with or without soluble p97 (100 nM). After 18 hours incubation, HMEC-1 cells were detached by incubation with PBS-citrate buffer (138 mM NaCl, 2.8 mM KCl, 1.47 mM KH 2 PO 4 , 8.1 mM Na 2 HPO 4 , 15 mM sodium citrate, pH 7.4). HMEC-1 (1×10 6 cells) were counted and resuspended in the binding buffer (10 mM Hepes, 140 mM NaCl, 2.5 mM CaCl 2 , pH 7.4). Cell suspension was then incubated at 4° C. for 15 minutes with anti-u-PAR antibody #3937 (1 μg/mL), anti-α-LRP antibody (8G1 clone) (1 μg/mL) or with a non-specific IgG1 (1 μg/mL). The cells were then washed with binding buffer and incubated in the dark at 4° C. for 15 minutes with goat anti-mouse Ig-Alexa488 (1 μg/mL) (Molecular Probes, Eugene, Oreg.). After two washes with binding buffer, the cells were analyzed by flow cytometry on a Becton Dickinson FACscan™ with a 488 nM Argon laser using predetermined instrument settings. Cell surface levels of u-PAR and α-LRP, corrected for the background fluorescence intensity measured in the presence of a non-specific IgG1, were expressed as mean fluorescence intensities.
Cell Detachment Assay
[0091] HMEC-1 were plated into a 6-wells plate and placed at 37° C. in 5% CO 2 /95% air until confluence. Cells were then exposed to serum free medium containing 150 nM plasminogen and 4 nM tPA, with or without 100 nM of melanotransferrin in the presence or absence of 150 nM alpha2-antiplasmin, 1 μM EGCG or 10 μM Ilomastat. After 24 hours treatment HMEC-1 detachment was visualized at a 100× magnification using a digital Nikon Coolpix™ 5000 camera (Nikon Canada, Mississauga, ON) attached to a Nikon TMS-F microscope (Nikon Canada).
Human Plasma
[0092] Human blood samples were collected into a citrated Vacutainer® (Becton Dickinson, Franklin Lakes, N.J.) and centrifuged at 300×g for 5 minutes at 4° C. Plasma were aliquoted in eppendorfs and used fresh or frozen at −80° C. until used.
Thromboelastography Analysis
[0093] Thromboelastography analysis was performed with citrated plasma or artificial clot model using a computerized dual-channel thromboelastograph (TEG) analyzer (model 5000; Haemoscope Corp., Niles, Ill.). For the artificial clot model fibrinogen (8.2 μM), glu-plasminogen (3.3 μM) and tPA (4.5 nM) diluted in buffer A were transferred into the analyzer cups. Artificial clots were polymerized with thrombin (0.4 U/ml). For the plasma clot model, 350 μl of citrated plasma were transferred into the analyzer cups with tPA (4.5 nM). CaCl 2 (0.2 M) was added to initiate the polymerisation of plasma clot. The thromboelastograph analysis for both artificial and plasma clots were performed in the presence or absence of 1 μM p97.
Radial Clot Lysis Assay
[0094] Radial clot lysis assay was performed. Briefly, fibrin-clots were obtained by incubating fibrinogen (8.2 μM), glu-plasminogen (2 μM) and 0.4 μml of thrombin in buffer A at 37° C. for 60 min in a 6-wells plate. Clot lysis was initiated by dropping 2 μl of tPA (2 nM) with or without p97. Clots were incubated for 30 min at 37° C. and dyed with chinese ink. Photomicrographs at 40× magnification were taken using a digital camera Nikon Coolpix 5000 camera (Nikon Canada, Mississauga, ON) attached to a Nikon TMS-F microscope (Nikon Canada).
Data Analysis
[0095] Statistical analyses are made with the Student's paired t-test using GraphPad Prism (San Diego, USA). Significant difference is accepted for p values less than 0.05.
[0096] The present invention will be more readily understood by referring to the following examples which are given to illustrate the invention rather than to limit its scope.
Example I
Transcytosis of p97 through BBCEC Monolayers
[0097] Transcytosis experiments are performed at 37° C. for 2 hrs. [ 125 I]-p97 (25 nM) is added to the upper side of the cell-covered filter in the absence or presence of RAP (650 nM) or BSA (5 μM). At the end of the experiment, radiolabelled proteins are measured in the lower chamber of each well by TCA precipitation. Results represent means±SE (n=6) ( FIG. 1A ). In the second part of the experiment ( FIG. 1B ), p97 is immobilized on a sensor chip surface (CM5) as described in the Materials and Methods section above and p97, RAP and BSA (5 μg/100 μl) are injected over the immobilized p97.
[0098] The first evaluation was the transcytosis of p97 across an in vitro model of the BBB at 37° C. ( FIG. 1A ). A significant (>50%) reduction in the transport of [ 125 I]-p97 (25 nM) from the apical (blood side) to the basolateral side (brain side) of BBCEC monolayers was observed in the presence of 640 nM RAP. Transcytosis of [1251]-p97 was unaffected by a 200-fold molar excess of BSA. The permeability coefficient for sucrose is similar in the absence or presence of RAP indicating that the integrity of the BBCEC monolayers was unaffected by this protein. The results with RAP also indicate that LRP is involved in p97 transcytosis since it has been reported to be an LRP ligand, whereas BSA was shown to bind to megalin, another member of the LDL receptor family, probably via cubilin (Kozyraki R et al., 2001 Proc Natl Acad Sci USA 98:12491-12496). To determine whether protein interaction could occur between p97 and RAP, leading to a reduction in p97 transcytosis, protein interactions were investigated by using biological interaction analysis in real-time ( FIG. 1B ). For this analytical approach, p97 was first immobilized on the surface of a sensor chip. Using standard NHS/EDC coupling procedures about 8 to 10 ng/mm 2 of p97 were immobilized. RAP or BSA (0.05 μg/μl) were then injected over immobilized p97. No interactions could be observed between these proteins and p97, indicating that the inhibition of [ 125 I]-p97 transcytosis is not related to protein interactions between p97 and RAP.
Example II
Pro-uPA and p97 Interaction
[0099] Biospecific Interaction Analysis between p97 and anti-p97 mAbs
[0100] Biospecific interaction analysis in real-time between p97 and various anti-p97 mAbs is performed as follows. p97 is immobilized on a sensor chip (CM5) using standard coupling procedures incorporating NHS, EDC and ethanolamine. Different mAbs directed against p97 (HybC, HybE, HybF, L235, 2C7, 9B6), diluted to 0.05 μg/μl in Ringer/Hepes, are injected into the BIAcore at a flow rate of 5 μl/min. The surface plasmon resonance response obtained for these mAbs is plotted (in relative units (RU)) as a function of time. After each injection immobilized p97 is regenerated with 0.2M glycine at pH 2 for 2 min (n=4).
[0101] To evaluate the impact of immobilization procedures on the structural integrity of p97 different mAbs directed against various conformational epitopes of p97 were injected over p97 ( FIG. 2 ). The surface plasmon resonance (SPR) signal generated by the interaction between p97 and various mAbs varied from 250 relative units (RU) to 2500 RU. These data show that the mAbs could still recognize p97, indicating that the protein is intact following its immobilization on the sensor chip surface. Table 2 shows the kinetic parameters estimated by the BlAevaluation software for antibody interactions with p97. From these values, the affinity constant (K A =k a /K d ) of these mAbs for immobilized p97 ranged from 0.08 to 1.6 nM −1 and for the relative affinities are HybE<L235<9B6<2C7, HybC<HybF.
[0000] TABLE 2 Kinetics of interaction between immobilized p97 and mAbs. K a K d K A = K a /K d K D = K d /K a Antibodies ΔRU (M −1 s −1 ) (s −1 ) (M −1 ) (M) L235 1055 ± 82 4.4 × 10 4 5.3 × 10 −5 0.9 × 10 9 0.1 × 10 −10 HybC 1509 ± 184 7.2 × 10 4 4.5 × 10 −5 1.6 × 10 9 6.4 × 10 −10 HybE 232 ± 52 0.9 × 10 4 9.8 × 10 −5 0.08 × 10 9 0.01 × 10 −10 HybF 2199 ± 150 8.0 × 10 4 3.0 × 10 −5 2.7 × 10 9 3.8 × 10 −10 9B6 2440 ± 13 1.2 × 10 4 9.1 × 10 −5 1.3 × 10 9 7.9 × 10 −10 2C7 2290 ± 87 5.9 × 10 4 3.8 × 10 −5 1.6 × 10 9 6.5 × 10 −10 The difference between the relative units measured after and before injection of mAbs directed against p97 are presented (ΔRU) as well as the apparent association (K a ) and dissociation (K d ) constants. The affinity (K A ) and dissociation (K D ) constants were calculated from the K a and K d .
Molecular Interactions of p97 and Various Components of the PA:plasmin System
[0102] Determining the molecular interactions between p97 and various components of the PA:plasmin system was as follows. Pro-uPA and tPA (0.05 μg/μl), diluted in Ringer/Hepes, are injected onto immobilized p97 on a sensor chip at a flow rate of 5 μl/min. The SPR response for these proteins is plotted in RU as a function of time. p97 (0.05 μg/μl) is also injected over immobilized PAI-1 (p97/PAI-1). Plasminogen, plasmin or angiostatin (0.05 μg/μl) are also injected onto immobilized p97. The SPR response for these proteins is plotted in RU as a function of time. The results indicate that pro-uPA and plasminogen interact with p97. After each injection the sensor chip surface with immobilized p97 is regenerated by injecting 10 mM glycine, pH 2.2 for 2 min.
[0103] When pro-uPA and tPA (0.05 μg/μl) were injected over immobilized p97, protein interaction occurred between pro-uPA and p97 but not between tPA and p97 ( FIG. 3A ). About 8-10 ng/mm 2 of PAI-1 was also immobilized onto another well of a sensor chip surface using NHS/EDC coupling conditions. No interaction between p97 and immobilized PAI-1 could be detected ( FIG. 3A ). However a strong interaction could be observed when tPA was injected over PAI-1, indicating that PAI-1 can still interact with tPA following immobilization. In addition, plasminogen, plasmin and angiostatin (0.05 μg/μl) were injected over immobilized p97 ( FIG. 3B ). According to the SPR, plasminogen also interacts with immobilized p97 whereas plasmin and angiostatin, two plasminogen fragments, do not. The kinetic data obtained from binding of pro-uPA or plasminogen to immobilized p97 biosensor surface were evaluated using both the 1:1 Langmuir binding model and the two state conformational change model. Interestingly, the two state conformational change model was a better fit than the 1:1 Langmuir binding model when comparing a single concentration of either pro-uPA and plasminogen over p97 biosensor surface. Kinetic data obtained with the two state conformational model are presented in Table 3. Kinetic data for the interaction between pro-uPA and p97 shows an association constant (k a1 ) of 6.6×10 3 M −1 s −1 and a dissociation rate constant (k d1 ) of 1.7×10 −3 s −1 . Furthermore, the forward rate constant (k a2 =3.2×10 −3 s −1 ) and backward rate constant (k d2 =7.1×10 −4 s −1 ) for the conformational change provide an apparent equilibrium dissociation constant ((K D =k d1 /k a1 )/(k d2 /k a2 )) of 65 nM. The kinetic analysis of plasminogen interaction with p97 shows an association constant (k a1 ) of 2.1×10 4 M −1 s −1 . The dissociation rate constant (k d1 =4.3×10 −2 s −1 ), as well as the forward rate constant (k a2 ) of 6.0×10 −2 s −1 and backward rate constant (k d2 ) of 1.1×10 −3 s −1 , are different from those seen for the pro-uPA interaction with p97. However, the apparent equilibrium dissociation constant (K D ) between p97 and plasminogen is 350 nM, which is different from that observed for the interaction of pro-uPA with immobilized p97.
[0000]
TABLE 3
Kinetics of interaction between immobilized p97 and pro-uPA or plasminogen
using the two state conformational model
Immobilized
k a1
k a2
k d1
k d2
KD
proteins
Ligands
(×10 4 M -1 s -1 )
(×10 −3 s -1 )
(×10 −3 s -1 )
(×10 −4 s -1 )
(×10 −9 M)
p97
pro-uPA
66.2
3.2
6.0
7.1
65
plasminogen
2.1
6.0
3.1
11.2
350
[0104] Kinetic parameters of Table 3 were based on a two state conformational change binding model using the biosensorgram shown in FIG. 3 . This model describes a 1:1 binding of analyte to immobilized ligand followed by a conformational change in the complex. It is assumed that the conformationally changed complex can only dissociate through the reverse of the conformational change: A+B=AB=ABx. The dissociation constants (K D ) were derived using both association (ka) and dissociation (k d ) rates (K D =(k d1 /k a1 )×(k d2 /k a2 ). The parameters are: k at , association rate constant for A+B1=AB1 (M −1 s −1 ); k d1 , dissociation rate constant for AB1=A+B1 (s −1 ); k a2 , forward rate constant for AB=ABx (s −1 ); k d2 , backward rate constant for AB=ABx (s −1 ). The mean Chi 2 values for the sensorgram fits were less than 0.4.
[0000] Effect of p97 on pro-uPA, tPA and Plasminogen
[0105] To evaluate the effect of p97 interaction on pro-uPA, tPA and plasminogen, the serine activity (VLK-pNA hydrolysis) of 90 nM pro-uPA and 75 nM tPA were measured in the absence (o) or presence () of 70 nM p97 without plasminogen using a colorimetric assay, both with and without p97 ( FIGS. 4A and 4B ). The reaction was performed in a final volume of 200 μl as described in the Materials and Methods section above. In both FIGS. 4A and 4B , controls were also performed with p97 (▪) but without pro-uPA or tPA (n=9, for pro-uPA; n=6, for tPA). In the absence of p97, only a slight activity was measured for both pro-uPA and tPA. However, the VLK-pNA hydrolysis by pro-uPA goes from less than 50 AU/min in the absence of p97 to more than 450 AU/min when p97 is added into the incubation ( FIG. 4A ). Addition of p97 to tPA elicits no observable effect and p97 alone had no proteolytic activity ( FIG. 4B ). The results from both SPR and enzymatic activity indicate that the change in pro-uPA conformation induced by p97 increased its ability to degrade the plasmin substrate.
[0106] To determine whether interaction with p97 leads to a cleavage of pro-uPA, the proteins were co-incubated for 5 min. at 37° C. in the presence or absence of plasminogen. They were then separated by SDS-PAGE under reducing conditions using a 12.5% acrylamide gel and stained with standard Coomassie Blue. The results are shown in FIG. 4C . The lanes of the gel are as follows ( FIG. 4C ): 2 μg of p97 (lane 1), 1 μg pro-uPA (lane 2) and 2 μg plasminogen (lane 3) were incubated for 5 min. at 37° C. alone as controls. Pro-uPA (2 μg) was incubated at 37° C. for 5 min. with 2 μg of p97 (lane 4). Plasminogen and Pro-uPA were added without incubation (lane 5) and with 5 min. incubation at 37° C. (lane 6). Pro-uPA with 2 μg of both p97 and plasminogen were added without incubation (lane 7) or with 5 min. incubation at 37° C. (lane 8). Tc-uPA (2 μg) was also loaded as a control (lane 9). Under these conditions p97 and uPA migrated as 97 kDa and 33 kDa bands, respectively, whereas pro-uPA migrated as a single band at 55 kDa. No major degradation of either protein could be detected, indicating that the incubation of pro-uPA with p97 under the conditions used to perform the VLK-pNA hydrolysis did not cleave either protein. Even after 6 hours incubation at 37° C., both proteins were stable. In the presence of plasminogen, pro-uPA was cleaved after an incubation of 5 min. at 37° C. and two major fragments of 33 kDa and 29 kDa could be observed. When p97 was added to the incubation medium, the generation of these fragments did not change.
[0107] The impact of p97 on plasminogen fragmentation by pro-uPA was further estimated using 6 hours incubation at 37° C. and the results are shown in FIG. 4D . The lanes of the gel are as follows: 3 μg of p97 (lane 1), glu-plasminogen (lane 2) and lys-plasminogen (lane 3) were incubated alone for 6 hours at 37° C. as controls. In lane 4, 34 of both glu-plasminogen and p97 were also incubated for 6 hours at 37° C. Pro-uPA (20 ng) was added to plasminogen for the same period of incubation at 37° C. (lane 5). p97 was added to pro-uPA and plasminogen for 6 hours at 37° C. (lane 6) or 4° C. (lane 7). In lane 8, 3 μg of angiostatin (lane 8) was also added as a control. Proteins were separated on a 7.5% acrylamide gel under non-reducing conditions and stained with Coomassie blue. When p97 is added to glu-plasminogen no apparent fragment was generated. In contrast, the addition of a low amount (10 ng) of pro-uPA, which could not be detected using standard Coomassie blue staining, induced degradation of Glu-plasminogen with the appearance of fragments which migrated at the same molecular weight as Lys-plasminogen. Moreover, when p97 is added to glu-plasminogen and pro-uPA, the degradation profile of glu-plasminogen is changed. In the presence of p97 with glu-plasminogen and pro-uPA, higher levels of bands migrating at the same molecular weight as lys-plasminogen were observed and two other fragments appeared at 50 and 30 kDa. These fragments do not seem to be related to angiostatin since they migrated at a different molecular weight than did the control angiostatin at 42 kDa. These results indicate that p97 alters the cleavage of glu-plasminogen by pro-uPA.
Example III
Plasminogen Activation by p97
[0108] The interaction of p97 with pro-uPA was further characterized by measuring the activation of plasminogen by pro-uPA in the presence of p97 ( FIG. 5 ). The plasminolytic activity of 1 nM uPA was measured without (o) or with () 70 nM p97 in the presence of 30 nM plasminogen. The reaction was performed in a final volume of 200 μl as described in the Materials and Methods section above. As a control, the enzymatic activity in the presence of p97 alone was also measured (▪). When p97 is added to pro-uPA and plasminogen, the VLK-pNA hydrolysis is 4-fold higher after 180 min ( FIG. 5A ). Control experiments performed with p97 indicated that this protein alone does not generate plasmin when it is added to plasminogen.
[0109] The plasmin activity in the presence of various concentrations of p97 was also measured ( FIG. 5B ). Plasmin activity induced by pro-uPA was measured in the presence of various p97 concentrations. Since the generation of plasmin proceeds at a constant rate under the assay conditions used, plotting the experimental data as a function of time (t) 2 allowed for the determination of the initial rate of plasmin formation. From these linear curves, the initial plasmin activity measured in the absence of p97 was subtracted from the activities obtained in the presence of various p97 concentrations. Thus, the data represent the initial rates of plasmin activity (corresponding to the slopes) in the presence of various p97 concentrations. p97 stimulates the plasminogen cleavage by pro-uPA in a dose-dependent manner with half-maximal stimulation occurring at 25±6 nM.
[0110] The effect of p97 on plasmin activity in the presence of various concentrations of plasminogen was also measured ( FIG. 5C ). Plasmin activity induced by pro-uPA was measured without (o) or with () 250 nM p97 and various concentrations of plasminogen. Initial rates of plasmin activity calculated at several plasminogen concentrations were plotted as a function of plasminogen concentrations. The resulting experimental data were fitted using nonlinear regression analysis. p97 decreased the apparent Km of pro-uPA for plasminogen from 188±22 to 102±17 nM and increased the Vmax from 6.9±0.4 to 8.9±0.6 AU/min. These results indicate that p97 positively affects the activation of plasminogen by pro-uPA by increasing the catalytic efficiency by a factor of 2.4-fold.
[0111] To determine whether the induction of plasmin formation by p97 was specific, the formation of plasmin by pro-uPA in the presence of either the mAb L235 (directed against p97) or a non-specific IgG was measured ( FIG. 5D ). The plasminolytic activity of pro-uPA was measured in the presence of 70 nM p97 and 65 nM of either mAb L235 (o) or non-specific mouse IgG (). One representative experiment is shown and data represent the means±SD of values obtained from triplicates (n=3). MAb L235 (50 nM) inhibited the pro-uPA activation induced by p97 by 50%. These results indicate that the effect of p97 upon pro-uPA's activation of plasminogen is specific and involves the epitope recognized by the mAb L235.
Example IV
Inhibition of Cell Migration by mAb L235
[0112] Since p97 affects the activation of plasminogen in vitro and since the uPA/uPAR system is important in cell migration, it was further investigated whether endogenous p97 might be associated with this process. Cell migration of HMEC-1, SK-MEL28 cells or HUVEC was measured using modified Boyden chambers as described in the Materials and Methods section above. Because p97 was first identified in melanoma cells (Brown J P et al., 1981 Proc Natl Acad Sci USA 78:539-543), the impact of the mAb L235 on the migration of human melanoma (SK-MEL28) cells was also measured ( FIG. 6A ). Cells that had migrated to the lower surface of the filters were fixed and stained with crystal violet. Images obtained from a representative experiment are shown. Cells that had migrated in the presence of 50 nM mAb L235 or a non-specific mouse IgG were also counted. The results were expressed as the percentage of the control measured in the presence of a non-specific mouse IgG and represent the means±SD (n=5 for HMEC-1; n=4 for SK− MEL28; n=3 for HUVEC). Statistically significant differences are indicated by ***p<0.001 (Student's t-test). In the presence of mAb L235 (50 nM), the migration of HMEC-1 and SK-MEL28 cells was inhibited by 54% and 48%, respectively. However, cell migration of HUVEC was unaffected by this concentration of mAb L235.
[0113] Endogenous p97 was immunodetected in lysates or serum-deprived culture media (18 hours) from HMEC-1, SK-MEL28 and HUVEC cells. FIG. 6B shows the detection of endogenous p97 by Western blot analysis. Proteins were separated by SDS-PAGE and were electrophoretically transferred to PVDF membranes. p97 was detected by Western blotting using mAb L235 and a secondary anti-mouse IgG linked to peroxidase. p97 migrated under unreduced conditions at 73 and 60 kDa, as previously observed. It was highly expressed in lysates from HMEC-1 and SK− MEL28 cells and at lower levels in their respective conditioned culture media. In HUVEC cells, p97 was however almost undetectable. In fact, the exposure time was at least 30 times greater to detect a much lower level of p97 in HUVEC compared to HMEC-1 and SK-MEL28 cells. These results indicate that mAb L235, by interacting with endogenous p97, inhibits the migration of HMEC-1 and SK-MEL28 cells. This also indicates that the endogenous p97 in these cells is involved in cell migration.
Example V
Effect of Exogenous p97 on Cell Migration
[0114] It was also estimated whether exogenous p97 could affect the migration of HMEC-1 and SK-MEL28 cells. HMEC-1 and SK-MEL28 cell migration was performed using modified Boyden chambers as described in the Materials and Methods section above. Cells that had migrated in the presence or absence of p97 (100 nM) to the lower surface of the filters were fixed and stained with crystal violet. The results are shown in FIGS. 7A and 7B . Cells that had migrated were also counted and expressed as a percentage of the control cells, measured in the absence of p97 (n=4, for HMEC-1; n=3, for SK-MEL28). Exogenous p97, at 10 nM and 100 nM, inhibited the migration of HMEC-1 cells by 34% and 50% ( FIG. 7C ). The migration of SK-MEL28 cells was inhibited by 44% and 70% in the presence of 10 and 100 nM p97. Migration of HUVEC cells was unaffected by these concentrations of p97. Moreover, this inhibition of cell migration is not related to a reduction of endothelial or melanoma cell adhesion since the same concentrations of p97 did not affect adhesion on gelatin of either HMEC-1 or SK-MEL28 cells.
Example VI
Inhibition of Plasminolytic Activity at the Cell Surface by Soluble p97 and mAb L235
[0115] The effect of p97 on plasminolytic activity was determined as follows. HMEC-1 cells were treated for 18 hours with 100 nM p97 (+p97) or Ringer solution (Control). Following this treatment the plasminolytic activity was measured using standard conditions, as described in the Materials and Methods section above. When cells were treated with p97 (100 nM), plasminogen activation was inhibited by 95% ( FIG. 8A ). This marked reduction in the plasminolytic capacity of these cells by soluble p97 could explain the inhibition of HMEC-1 migration. The effect of mAb L235 on plasminolytic activity of HMEC-1 was also determined. HMEC-1 cells (1×10 5 cells) were pre-incubated 1 hr. at 37° C. with Ringer solution (Ctl) or with 250 nM of either mAb L235 or non-specific mouse IgG. Following this pre-incubation, the plasminolytic activity was measured for 6 hrs by adding pro-uPA (1 nM) and plasminogen (50 nM) using standard conditions, as described in the Materials and Methods section. The plasminolytic activity of HUVEC was also measured using 1×10 5 cells under the same conditions. Data represent the means±SD of three independent experiments performed in triplicate. Statistically significant differences are indicated by *** where p<0.001 (Student's t-test). When HMEC-1 cells were treated with the mAb L235, the plasminolytic activity was inhibited by more than 50% compared to non-specific mouse IgG ( FIG. 8B ). This inhibition by the mAb L235 indicates that endogenous, membrane-bound p97 participates in plasminogen activation in HMEC-1.
Example VII
Anti-Angiogenic Properties of p97
[0116] Angiogenesis, a complex multistep process that leads to the outgrowth of new capillaries from pre-existing vessels, is an essential mechanism in wound healing, embryonic development, tissue remodeling, and in tumor growth and metastasis. This process involves EC proliferation, migration and morphogenic differentiation into capillary-like structures. One of the key elements in cell migration is the urokinase-type plasminogen activator receptor (u-PAR). The plasminogen activator (PA) family is composed of urokinase-type plasminogen activator (u-PA) and tissue-type plasminogen activator (t-PA); their inhibitors are the plasminogen activator inhibitor type 1 and 2 (PAI-1; PAI-2). u-PAR mediates the internalization and degradation of u-PA/inhibitor complexes via the low-density lipoprotein receptor-related protein (LRP), whereas LRP mediates the internalization and degradation of t-PA/inhibitor complexes. Thus, the u-PAR/LRP system controls cell migration by regulating plasminogen activation by PAs at the cell surface. PAs are therefore involved in angiogenesis by enhancing cell migration, invasion and fibrinolysis. Moreover, plasminogen needs to be first converted to the two-chain serine protease plasmin. When Glu-plasminogen, the native circulating form of the zymogen, is bound to the cell surface, plasmin generation by PAs is markely stimulated compared with the reaction in solution. Optimal stimulation of plasminogen activation at the EC surface requires the conversion of Glu-plasminogen to Lys-plasminogen.
[0117] Since soluble p97 interacts with plasminogen and single-chain u-PA (scu-PA), the potential role of soluble p97 on angiogenesis was further investigated. Herein, it is shown that soluble p97 inhibits EC migration and tubulogenesis by affecting both u-PAR and LRP expression as well as the binding of the u-PA•PAI-1 complexe at the cell surface of human microvessel EC (HMEC-1). To further understand the impact of soluble p97 on morphogenic differentiation of EC into capillary-like structures, the expression of key players associated with angiogenesis was also determined.
Cell Culture
[0118] Cells were cultured under 5% CO 2 /95% air atmosphere. Human dermal microvessel endothelial cells (HMEC-1) were from the Center for Disease Control and Prevention (Atlanta, Ga.) and were cultured in MCDB 131 supplemented with 10 mM L-glutamine, 10 ng/ml EGF, 1 μg/ml hydrocortisone and 10% inactivated foetal bovine serum (FBS). HUVECs was obtained from ATCC (Manassas, Va.). HUVECs were cultured in EGM-2 medium (bullet kit, Clonetics #CC-3162) and 20% inactivated FBS.
Enzymatic Assay
[0119] The enzymatic activity of p97, sc-uPA, uPA and tPA was measured using a colorimetric assay ( FIG. 9 ). The reaction was performed in a final volume of 200 μL in an incubation medium consisting of 50 nM Tris/HCl buffer (pH 7.5), 150 mM NaCl and 50 mM CaCl 2 . This incubation medium also contained 15 μg/mL L-val-leu-lys-p-nitraniline (VLK-pNA) and 25 nM glu-plasminogen. The enzymatic activity was assessed with or without 100 nM soluble p97. The reaction was started by the addition of 1 nM sc-uPA, uPA or tPA. In this assay, the cleavage of VLK-pNA results in a p-nitraniline molecule that absorbs at 405 nm. The reaction product was monitored at 405 nm using a Microplate Thermomax Autoreader™ (Molecular Device, CA).
Western Blot Analysis
[0120] In FIG. 10 , HMEC-1 (3×10 6 cells) were plated into a 75 cm 2 culture flask with fresh medium with or without 10 and 100 nM of p97. After 18 hours treatment, HMEC-1 were washed twice PBS Ca +2 /Mg +2 free and solubilized in lysis buffer (1% Triton-X-100™, 0.5% NP-40, 150 mM NaCl, 1 mM EDTA, 10 mM Tris, 2% N-octylglucoside, 1 mM orthovanadate, pH 7,5) for 30 minutes on ice. Supernatant proteins were measured using a micro-BCA (bicinchonic acid) kit (Pierce). Conditioned media and cell lysates of HMEC-1 were subjected to SDS-PAGE using 5% acrylamide gel for the detection of α-LRP, 10% acrylamide gel for the detection of uPAR. Separated protein were transferred electrophoretically from polyacrylamide gel to PVDF transfer membrane (PerkinElmer Life Sciences) in a Minitrans-Blot™ cell (Bio-Rad) for 90 minutes at 80 mA per gel. Following transfert, western blot analysis were performed. All immunodectection steps were carried out in Tris-buffered saline/0.1% Tween, pH 8.0 [TBS-Tw (0.1%)]. The primary antibody was diluted 1:250 for LRP and uPAR. The secondary antibody, horseradish peroxidase-conjugated anti-mouse IgG (Jackson), was diluted 1:2500 in 1% powdered skimmed milk in TBS-Tw. Incubation with enhanced luminol reagent (PerkinElmer Life Sciences) and exposure to x-ray film were used to determined protein levels
Capillary Tube Formation on Matrigel
[0121] In FIG. 11 , Matrigel was thawed on ice and added (50 μl) to a 96-well plate for 10 min at 37° C. HUVEC or HMEC-1 were harvested by trypsinization and spun down. About 25 000 cells were resuspended and added to Matrigel-coated wells for 30 min at 37° C. After cell adhesion, the medium was removed and 100 μl of fresh cell culture medium with or without p97 was added. Wells were then incubated for 18 hours at 37° C. After incubation, tubular structures were visualized using a Nikon TMS-F microscope (at a maginification of x40). The length of the capillary network was quantified using a map scale calculator.
[0122] In conclusion, as shown in FIG. 9 , p97 stimulates the plasminolytic activity of single chain urokinase plasminogen activator (sc-uPA or pro-uPA), uPA and tissue plasminogen activator (tPA) in vitro. In addition, as shown in FIG. 10 , low density lipoprotein related protein (LRP) and the urokinase activator receptor (uPAR) are down regulated in p97 treated MHEC-1 cells. Furthermore, as shown in FIG. 11 , HMEC-1 and HUVEC capillary tube formation is inhibited by low concentration of soluble p97.
[0000] Soluble p97 Inhibits the Morphogenic Differentiation of EC into Capillary-Like Structures
[0123] The process of angiogenesis is associated with the morphogenic differentiation of EC into microvascular capillary-like structures. To investigate this crucial step of angiogenesis, many studies have used an in vitro assay for tube formation on Matrigel. In the present invention, HMEC-1 and HUVEC cells growth on Matrigel generated a stabilized network of capillary-like structures. This is shown by the complexity of the tubular network per field in control cells observed after 18 hours. The effects of exogenous soluble p97 on HMEC-1 and HUVEC morphogenic differentiation was therefore determined into capillary-like structures ( FIG. 11 ). The generation of capillary-like tubular structure was strongly reduced when soluble p97 was added during the experiments. Indeed, soluble p97 at 10 and 100 nM reduced, by 53% and 47%, the capillary-like tube formation of HMEC-1 ( FIG. 11A ) and reduced, by 38% and 35%, the capillary-like tube formation of HUVECs ( FIG. 11B ). These results indicate that soluble p97 inhibits the initiation of capillary-like tube formation. In FIGS. 11A to 110 , data represent the means±SD of results obtained from three different experiments performed in triplicates. Statistically significant differences are indicated by **p<0.01, ***p<0.001 (Student's t-test). Photos (original magnification, X40) obtained from a representative experiment are shown.
Soluble p97 Modulates HMEC-1 Cell Migration
[0124] Since soluble p97 affected plasminogen activation, it first investigated whether soluble p97 might modulate cell migration. Using modified Boyden chamber, HMEC-1 cell migration was examined in the presence of soluble p97 ( FIG. 12A ). soluble p97, at 10 and 100 nM, inhibited the migration of HMEC-1 by 34% and 50%, respectively. The inhibition of HMEC-1 cell migration is completely lost when soluble p97 was boiled for 30 minutes at 100° C. prior to the migration assay ( FIG. 12B ). This result indicates that a native conformation of soluble p97 is required to inhibit HMEC-1 cell migration. The adhesion of HMEC-1 on gelatin was found unaffected by soluble p97 ( FIG. 12C ), indicating that the inhibition of cell migration is unrelated to a reduction of adhesive properties. In FIG. 12A ), HMEC-1 cell migration was performed using modified Boyden chambers as described in the Materials and Methods sections. Cells that had migrated in the presence or absence of soluble p97 to the lower surface of the filters were fixed, stained with crystal violet and counted. Results are expressed as a percentage of migration in soluble p97-treated cells compared to untreated cells. Data represent the means±SD of four independent experiments performed in triplicates. (B) HMEC-1 cell migration was performed as indicated previously with native or boiled soluble p97. Data represent the means±SD of two independent experiments performed in triplicates. (C) HMEC-1 cell adhesion was performed on gelatin as described in the Materials and Methods sections. Cells that had adhered to the gelatin in the presence or absence of soluble p97 were stained with crystal violet. Results are expressed as a percentage of adhesion in soluble p97-treated cells compared to untreated cells. Data represent the means±SD of three independent experiments performed in triplicates. In all experiments, statistically significant differences are indicated by ***p<0.001 (Student's t-test) (original magnification, X100).
[0000] Soluble p97 Up-Regulates u-PAR and LRP Protein Expression
[0125] To identify a potential mechanism by which soluble p97 inhibited in vitro EC migration and tubulogenesis, the effect of soluble p97 on the protein expression of both the u-PAR system and LRP was measured by Western blot ( FIG. 13 ). HMEC-1 cells were incubated for 18 hours with or without soluble p97. GAPDH was immunodetected to ensure that the protein content between samples was equivalent. Soluble p97 treatment significantly down-regulated u-PAR and LRP expression. In fact, exposure of HMEC-1 to soluble p97 at 10 and 100 nM reduced u-PAR expression in cell lysates by 20% and 40%, respectively ( FIG. 13A ). The same concentrations decreased LRP expression by 20% and 50%, respectively ( FIG. 13B ). In FIGS. 13A and 13B , HMEC-1 were treated for 18 hours with or without soluble p97. Following this treatment, proteins from cell lysates were resolved by SDS-PAGE. Immunodetections of u-PAR ( 13 A) and LRP ( 13 B) were performed as described in the Materials and Methods section. Results were expressed as a percentage of protein expression detected in soluble p97-treated cells compared to untreated cells. Data represent the means±SD of results obtained from three different experiments. Statistically significant differences are indicated by *p<0.05, ***p<0.001 (Student's t-test).
[0000] Soluble p97 Unaffects the u-PAR/LRP System mRNA Expression
[0126] Since soluble p97 modulated u-PAR and LRP protein expression, the mRNA expression of LDL-R family gene and u-PAR were estimated by RT-PCR in HMEC-1 treated or not with soluble p97 ( FIG. 14 ). In FIG. 14 , HMEC-1 were treated for 18 hours with or without soluble p97. Total RNA was isolated from HMEC-1 and gene products were amplified by RT-PCR as described in the Materials and Methods section. Table 4 shows the primer sequences used for specific cDNA amplification. Expression of the different members of the LDL-receptor family was first investigated in untreated HMEC-1 cells. Under the conditions used for RT-PCR analysis, LRP, LRP 1B, LDL-R and LRP 8 were clearly amplified (35 cycles) whereas LRP 2 and LRP 5 products were almost undetectable. Following soluble p97 treatment, the mRNA levels of LRP, LRP 1B, LRP 2, LDL-R, LRP 8 or u-PAR was unchanged in treated cells as compared to control cells ( FIG. 14 ). An internal control, GAPDH mRNA, was also unaffected by soluble p97. Since u-PAR and LRP gene expression were unaffected by soluble p97, these results indicate that soluble p97 effects on u-PAR and LRP expression takes place at the protein level.
[0000] Soluble p97 Modulates the Cell Surface Levels of u-PAR and LRP
[0127] In view of the fact that u-PAR and LRP expression is affected by exogenous soluble p97 and that the amount of u-PAR and LRP at the membrane surface is a key element in plasmin formation, the u-PAR and LRP levels at the cell surface was determined by FACS analysis following soluble p97 treatment ( FIGS. 15A and 15B ). HMEC-1 cells were incubated for 18 hours with or without 100 nM of soluble p97. Flow cytometric analysis of cell surface u-PAR ( 15 A) and LRP ( 15 B) levels was performed as described in the Materials and Methods section. Control (grey line:1) or treated HMEC-1 (bold line:2) were labeled with anti-u-PAR antibody (#3937) or with anti-α-LRP antibody (clone 8G1) and detected with goat anti-mouse IgG-Alexa488. These results are representative of three different experiments. Results were corrected for the background fluorescence intensity measured with a non-specific IgG1 and expressed as mean fluorescence intensities. Data represent the means±SD of three different experiments. Statistically significant differences are indicated by ** p<0.001, ***p<0.001 (Student's t-test). The mean fluorescence intensity associated with the detection of cell surface u-PAR is significantly higher by 25% following soluble p97 treatment. Cell surface LRP expression was also assessed by FACS analysis as in control (grey line:1) and treated cells (bold line:2) ( FIG. 15B ).
[0128] In FIG. 15C , following cell treatment with soluble p97, binding of 125 I-uPA•PAI-1 complexe was performed as described in the Materials and Methods section. Data represent the means±SD of three different experiments. Statistically significant differences are indicated by ***p<0.001 (Student's t-test).
[0129] The mean fluorescence intensity associated with the detection of cell surface LRP is significantly lower by 30% following soluble p97 treatment. These results suggest that soluble p97 treatment significantly increased u-PAR levels and decreased LRP levels at the cell surface of HMEC-1. To find out whether u-PAR at the cell membrane of HMEC-1 soluble p97-treated cell is free or occupied by u-PA and/or uPA•PAI-1 complexe, a binding assay of 125 I-uPA•PAI-1 complexe on HMEC-1 following soluble p97 treatment ( FIG. 15C ) was next performed. HMEC-1 were incubated for 18 hours with or without soluble p97 and the binding of 125 I-uPA•PAI-1 complexe was then measured at 4° C. in control and treated cells. The cell associated radioactivity after the binding of 125 I-uPA•PAI-1 complexe was reduced by about 23% following soluble p97 treatment. This result suggest that the free u-PAR at the cell membrane was decreased after soluble p97 treatment.
[0000] Soluble p97 Up-Regulates Cav-1 and Down-Regulates pERK 1/2 Protein Expression.
[0130] To further understand the effects of soluble p97 on in vitro EC migration and tubulogenesis, the expression and phosphorylation levels of proteins associated with angiogenesis ( FIGS. 16 and 17 ) was next measured. In this invention, HMEC-1 were incubated for 18 hours with or without soluble p97 (10 or 100 nM). Following this treatment, proteins from cell lysates were solubilized and resolved by SDS-PAGE. Immunodetection of Cav-1 ( 16 A) and pCav-1 ( 16 B) as well as ERK 1/2 ( 16 C) and pERK 1/2 ( 16 D) was performed as described in the Materials and Methods section. Results were expressed as a percentage of protein expression detected in soluble p97-treated cells compared to untreated cells. Data represent the means±SD of results obtained from three different experiments. Statistically significant differences are indicated by ***p<0.001 (Student's t-test). Since Cav-1 play an important positive role in the regulation of EC differentiation, a prerequisite step in the process of angiogenesis, the effects of soluble p97 on the structural protein Cav-1 and its tyrosine phosphorylated state (pCav-1) was examined by Western blot analysis ( FIGS. 16A and 16B ). The Cav-1 level was increased by 50% and 37% following soluble p97 treatment in HMEC-1 at 10 and 100 nM, respectively ( FIG. 16A ). The pCav-1 levels remained however unchanged in soluble p97-treated HMEC-1 as compared to control cells ( FIG. 16B ). Because Cav-1 has been previously implicated as a tonic inhibitor of the ERK 1/2 MAP kinase cascade involved in angiogenesis, the effects of soluble p97 on ERK 1/2 protein expression and phosphorylation levels was evaluated by Western blot analysis ( FIGS. 16C and 16D ). The ERK 1/2 level was unchanged following soluble p97 treatment in HMEC-1 ( FIG. 16C ). In contrast, the pERK 1/2 level was significantly decreased by 25% and 40% following soluble p97 treatment in HMEC-1 at 10 and 100 nM ( FIG. 16D ), respectively. Thus, these results show that soluble p97 affects differently the expression of Cav-1 and ERK 1/2, two proteins involved in the setting of angiogenesis.
[0000] Soluble p97 Down-Regulated eNOS Protein Expression as well as VEGFR-2 and VEGF-A mRNA Expression.
[0131] Cav-1 is also known to be an endogenous inhibitor of eNOS, a protein related to many physiological and pathological functions, including angiogenesis. Since soluble p97 modulates Cav-1 expression, the effect of soluble p97 on eNOS protein expression was assessed by Western-blot analysis ( FIG. 17A ). Soluble p97, at 10 and 100 nM, reduced eNOS levels by about 30% and 50%, respectively. In FIGS. 17A and 17B , HMEC-1 were treated for 18 hrs with or without soluble p97. Following treatment, proteins from cell lysates were solubilized and resolved by SDS-PAGE. Immunodetection of eNOS ( 17 A) was performed as described in the Materials and Methods section. Results were expressed as a percentage of protein expression detected in soluble p97-treated cells compared to untreated cells. Data represent the means±SD of results obtained from three different experiments. Statistically significant differences are indicated by **p<0.01, ***p<0.001 (Student's t-test).
[0132] Furthermore, eNOS has been suggest to play a predominant role in VEGF-induced angiogenesis. Because immunodetected levels of eNOS are reduced in soluble p97-treated HMEC-1 cells, the effect of soluble p97 on the mRNA levels of VEGF-A and its receptor, the VEGFR-2 ( FIG. 17B ) was estimated by RT-PCR. Following an incubation of 18 hours with or without 100 nM soluble p97, soluble p97 reduced VEGFR-2 and VEGF-A mRNA levels in HMEC-1 cells. In FIG. 17B , following treatment, total RNA was isolated from HMEC-1 and gene products were amplified by RT-PCR as described in the Materials and Methods section. Results obtained from a representative experiments are shown (N=3). These results indicate that soluble p97 affects the expression of key players associated with angiogenesis, including the protein expression levels of eNOS as well as the mRNA levels of VEGFR-2 and VEGF-A.
[0133] The results presented herein suggest a mechanism by which soluble p97 inhibits HMEC-1 cell migration as well as HMEC-1 and HUVEC capillary-like tube formation. Soluble p97 could affect the turn-over of LRP and u-PAR leading to a decreased capacity of plasminogen activation at the cell surface ( FIG. 18 ). In addition, soluble p97 treatment affects EC phenotype by affecting Cav-1, pERK 1/2, eNOS, VEGF-A and VEGFR-2.
[0134] In FIG. 18 , the schematic representation summarizes the results obtained in the present study after soluble p97 treatment. {circle around (1)} soluble p97 treatment decreases the total u-PAR and LRP expression levels in cell lysates, as assessed by Western-blotting. {circle around (2)} Since the total LRP levels decreased, the cell surface level of LRP also decrease. It is well established that LRP mediates the internalization of u-PAR. {circle around (3)} Since cell surface LRP levels decreased, it was postulated that the LRP-mediated endocytosis of u-PAR also decreased. {circle around (4)} The diminished rates of u-PAR endocytosis increased the total u-PAR level at the cell surface, as assessed by FACS analysis. {circle around (5)} Since u-PAR is not internalized by LRP, soluble p97 decreased the free u-PAR level at the cell surface. {circle around (6)} The decreases free u-PAR level at the cell surface lead to a decreased capacity of EC to activate plasminogen. The net effect of soluble p97 treatment on the u-PAR/LRP system lead to an inhibition of EC migration and morphogenic differentiation of EC into capillary-like structure.
Soluble p97 Causes Endothelial Cell Detachment and Extracellular Matrix Degradation
[0135] So far, It has been shown herein that soluble p97 stimulates plasminogen activation both in vitro and on endothelial cells. Increased plasmin formation has been implicated in endothelial cell detachment. Therefore, the effects of soluble p97 on endothelial cell adhesion in the absence and presence of plasminogen ( FIG. 19 ) was studied. While soluble p97 or plasminogen alone did not induce cell detachment, co-treatment of the endothelial cells with plasminogen, tPA and soluble p97 resulted in an increase cell detachment compared to control or tPA and plasminogen combination ( FIG. 19A ). The plasminolytic activity measured in FIG. 19B , showed that it is strongly increased when soluble p97 is added to tPA and plasminogen. Immuodetections of plasminogen and plasmin ( FIG. 19C ) indicate that the addition of soluble p97 increases the generation of plasmin which lead to matrix degradation and cell detachment. In FIG. 19 , addition of soluble p97 stimulates HMEC-1 detachment ( 19 A) and plasminolytic activity in cell media ( 19 B) in presence of plasminogen and tPA. Photos (original magnification, ×100) obtained from a representative experiment are shown. In FIG. 19C , following the treatment with or without soluble p97, proteins from cell media were resolved by SDS-PAGE and immunodetection of plasminogen and plasmin was performed as described in the Materials and Methods section. Immunodetections obtained from a representative experiment are shown. Results were expressed as a percentage of protein expression detected. Data represent the means±SD of results obtained from three different experiments. Statistically significant differences are indicated by *p<0.05, ***p<0.001 (Student's t-test).
[0136] Inhibitors of plasmin (alpha2-antiplasmin) and MMPs (EGCG and Ilomastat) block the effects of soluble p97 on endothelial cell detachment ( FIG. 20A ). In FIG. 20A , HMEC-1 detachement was performed in presence of three different inhibitors, namely, α2-antiplasmin, EGCG, and ilomastat. Photos (original magnification, ×100) obtained from a representative experiment are shown. In FIG. 20B , following the treatments, plasminolytic activity in cell media was measured as described in the Materials and Methods section. Data represent the means±SD of results obtained from three different experiments. Statistically significant differences are indicated by *p<0.05, ***p<0.001 (Student's t-test). The observed detachment of endothelial cells is mediated by extracellular matrix degradation. As an important component of the extracellular matrix involved in cell attachment, fibronectin is degraded by MMPs.
[0137] Fibronectin degradation was studied in lysates of soluble p97-treated endothelial cells by Western blotting. Whereas only small amounts of fibronectin degradation products were generated in the presence of plasminogen alone, co-treatment with tPA and soluble p97 potently increased fibronectin degradation ( FIG. 21 ). In FIG. 21 , HMEC-1 lysate from soluble p97 stimulated detachment were resolved by SDS-PAGE and immunodetection of fibronectin was performed as described in the Materials and Methods section. Immunodetections obtained from a representative experiment are shown. Results were expressed as a percentage of protein expression detected.
[0138] Overall, these results ( FIGS. 20 and 21 ) indicate that soluble p97 stimulates plasmin- and MMP-dependent endothelial cell detachment.
[0139] Consequently, these are the first data indicating that exogenous human recombinant soluble p97 have anti-angiogenic properties, by affecting the morphogenic differentiation of EC into capillary-like structures, by interfering with key proteins involved in angiogenesis and by inducing EC detachment.
Example VIII
Melanotransferrin Increases Human Blood Clot tPA-Fibrinolysis
[0140] Regulation of plasminogen is a key element in blood clot fibrinolysis. In the present invention, potential interactions between human recombinant p97 with components of the plasminogen activator system in relation with fibrinolysis were investigated. By using biospecific interaction analysis, it is demonstrated herein that p97 interacts with immobilized plasminogen. Kinetics analysis of the biosensorgrams using two state conformation change model shows an apparent equilibrium dissociation constant K D of 2.6×10 −7 M for this interaction ( FIG. 22 ). Moreover, soluble p97 increased the tPA-dependent plasminogen activation. This induction by p97 is inhibited by the monoclonal antibody L235 directed against p97 indicating that the increase in the plasminolytic activity is specific to p97 ( FIGS. 23A , 23 B and 23 C). p97 also enhanced the tPA fibrinolysis of plasma and fibrin clots ( FIG. 26 ). The thromboelastography of fibrinolysis and clot strength were evaluated with or without p97 ( FIG. 26 ). Complete lysis time (CLT) was reduced in the IVM (in vitro model) and plasma by 50% and 20% respectively when p97 was added to tPA. There was also a difference in the fibrinolysis by tPA at 30 min (LY30) in both models when p97 was added. The LY30 was enhanced by 5- and 2-fold in both artifical and blood clots, respectively. These results indicates that p97, by interacting with plasminogen, enhanced plasminogen activity by tPA reduced time of thrombolysis. In conclusion, these results demonstrate the potential of the present invention in new treatments of arterial disease and thrombosis and to reduce the damages to occluded hearth tissues.
[0000] Interaction between p97 and Plasminogen Using Biospecific Interaction Analysis in Real-Time
[0141] Plasminogen was immobilized on BIAcore with standard coupling procedures. Various concentrations of p97 were injected over immobilized plasminogen. The estimated constant of dissociation (K D ) estimated from these curves for the interaction between p97 and immobilized plasminogen is 275 nM. The results of this experiment are shown in FIG. 22 .
[0000] Melanotransferrin (p97) Increases the Plasminogen Activation by Tissue Plasminogen Activator (tPA)
[0142] Hydrolysis of the peptide VKL was measured in the presence of p97 alone, tPA and tPA+p97. As shown in FIG. 23A , in the presence of p97 the plasminogen activation by tPA was increased by 4-fold. As shown in FIG. 23C , the plasminogen activation by tPA was increased in a dose-dependent manner by p97 with half-maximal stimulation occurring at 12±3 nM.
Inhibition of the p97 Effect by the Monoclonal Antibody L235
[0143] The plasmin activity was measured in the presence of tPA and p97 with the monoclonal antibody directed against p97 (mAb L235) or a non-specific mouse IgG (mouse IgG). As shown in FIG. 23B , the induction caused p97 of the plasminogen activation by tPA is inhibited by the monoclonal antibody directed against p97 indicating that this induction is specific to p97.
p97 Increases Clot Fibrinolysis Induced by tPA
[0144] The effect of p97 on fibrinolysis was measured using a thromboelastograph. In the thromboelastography analysis (TEG), 320 μl of citrated plasma or artificial clot model (8.2 μM fibrinogen, 2 μM glu-plasmingen and 0.4 μml thrombin) was transferred into analyser cups with tPA (4.5 nM) and in the presence or absence of p97 (1 μM). The cups were placed in computerized dual-channel TEG analyzer (model 5000; Haemoscope Corp., Niles, Ill.). In one of the cups (channel 1), tPA was added, in another cup (channel 2) p97 and tPA were added. All cups containing 20 μl 0.2M CaCl 2 were prewarmed to 37° C. and analyzed simultaneously. The TEG variables collected from each sample included: CLT (clot lysis time), G (clot strength or Shear elastic modulus in dyn/s 2 , defined as G=(5000 A)/(100-A)), LY30 and LY 60 (percent of clot lysis at 30 and 60 min after maximum clot strength is achieved). As shown in FIG. 26A , when p97 was added to the artificial clot, the clot lysis at 30 min was increased by 5-fold. As shown in FIG. 26B , in the presence of p97, the lysis at 30 min of human blood clot by tPA was increased by 2-fold.
[0145] Because soluble p97 interacts with glu-plasminogen, the inventors have investigated whether human recombinant p97 might affect fibrinolysis and clot permeation. To show that soluble p97 could modulate fibrinolysis, the impact of human recombinant soluble soluble p97 on plasminogen activation by tPA ( FIG. 23A ) was first determined. After 180 minutes, the addition of soluble p97 increased by 6-fold the plasminogen activation by tPA measured by the hydrolysis of the VLK-peptide. Soluble p97 alone has no proteolytic or plasmin-like activity. The induction of tPA-dependent plasminogen activation by soluble p97 was also measured in the presence of the mAb L235 directed against soluble p97 or a non-specific IgG ( FIG. 23B ). The mAb L235, at 50 nM, inhibited by 80% the effect of soluble p97 on plasminogen activation by tPA. These results suggest that the effect of soluble p97 on plasminogen activation is rather specific and involves the conformational epitope recognizes by the mAb L235. In addition, plasmin activities measured as a function of time allowed us to extract initial rates. These rates were plotted as a function of soluble p97 concentrations ( FIG. 23C ). Soluble p97 stimulated the tPA-dependent conversion of plasminogen to plasmin in a dose-dependent manner with half-maximal stimulation occurring at 53±22 nM. The effect of soluble p97 on plasmin formation by tPA in the presence of various concentrations of plasminogen ( FIG. 23D ) was further evaluated. Initial rates of plasmin activity plotted as a function of plasminogen concentrations indicate that soluble p97 decreases the apparent K m of tPA for plasminogen by 5-fold from 280 to 52 nM. In FIG. 23A , the plasminolytic activity of tPA (60 ng) was measured without (∘) or with 1 μg/ml p97 () in the presence of Plg (0.5 μg). The reaction was performed in a final volume of 200 μl as described in the Materials and Methods section. The plasminolytic activity in the presence of p97 alone was also measured (▪). In FIG. 23B , the plasminolytic activity of tPA was measured in the presence of p97 (5 μg/ml) and either the mAb L235 (∘) or a non-specific mouse IgG (). The reaction was performed in a final volume of 200 μl as described in the Materials and Methods section. In FIG. 23C , plasmin activity induced by tPA was determined by measuring VLK-hydrolysis in the presence of various p97 concentrations. In FIG. 23D , initial rates of VLK-hydrolysis during Plg activation by tPA were measured without (∘) or with 50 nM p97 () in the presence of various concentrations of Plg. Data are shown as means of 3 experiments.
[0146] To further characterize the soluble p97 effects on the action of tPA in fibrinolysis, the effect of soluble p97 on a radial tPA-fibrinolysis assay ( FIG. 24 ) was evaluated.
[0147] The addition of soluble p97 to tPA enhances its action and leads to an increase perforation of the fibrin-clot ( FIG. 24A ). Surprisingly, in this experiment performed without tPA, soluble p97 in the presence of plasminogen creates a perforation of the fibrin-clot. Moreover, the size of the perforation increases as a function of soluble p97 concentration ( FIG. 24B ). In absence of plasminogen and tPA, the fibrin-clot is unaffected by soluble p97 alone. To determine whether soluble p97 has an intrinsic fibrinolytic activity, the release of fibrin fragments from clots labeled with [ 125 I]-fibrin ( FIG. 24C ) was measured. In spite of its ability to perforate the clot, soluble p97 alone does not generate [ 125 I]-fibrin fragments. However, soluble p97 in the presence of plasminogen increases the release of [ 125 I]-fibrin fragments by 2.5 fold following plasminogen activation by tPA.
[0148] The impact of soluble p97 on clot fibrinolysis by tPA was also measured ex vivo ( FIG. 25 ). The addition of soluble p97 increases by 2.5-fold the action of tPA. In FIG. 25 , the fibrinolytic activity of tPA (1 nM) on plasma clot fibrinolyis was measured ex vivo in the presence of increasing concentrations of p97.
[0149] In the blood coagulation system, the tissue-type plasminogen activator (tPA) is associated with fibrinolysis. tPA, mainly express by endothelial cells, cleaves the circulating plasminogen to the active proteinase plasmin which is the major enzyme responsible for the proteolytic degradation of the fibrin fiber. Currently, tPA is a stroke therapy which efficacy may be limited by neurotoxic side effects. Since soluble p97 potentialize plasminogen activation by tPA, the impact of soluble p97 on clot formation and lysis by thromboelastography analysis (TEG) has been evaluated using first an artificial fibrin-clot model ( FIG. 26A ). This model allowed to monitor the effect of soluble p97 on tPA-fibrinolysis in the absence of plasmin inhibitor. The fibrin clot is formed by the action of thrombin on fibrinogen and this clot also contains glu-plasminogen (2 μM). In FIG. 26 , representative tracing showing effects of p97 (1 uM) on the fibrinolysis of clot formation under shear by TEG. In FIG. 26A illustrates a thrombelastogram of the fibrin clot model and FIG. 26B illustrates a Thromboelastogram of plasma recalcified after addition of 2 mM CaCl 2 . The results shown here are representative of 3 experiments. The monitoring of the TEG paramaters indicates that the addition of soluble p97 increases the thrombolytic activity of tPA (Table 4). In particular, when soluble p97 (1 μM) is added to tPA, the lysis of the clot after 30 min (LY30) after its complete formation is 5 times higher whereas the complete lysis time (CLT) is 50% shorter. The impact of soluble p97 on fibrin-clot dissolution using human citrated plasma ( FIG. 26B ) was further evaluated. For these analysis, CaCl 2 is added to initiate the polymerisation of plasma clot. The TEG parameters obtained for these experiments (Table 4) indicate that the addition of soluble p97 to tPA causes a 30% decrease in the clot strength (G), increases twice the fibrinolysis rate and reduces the CLT by 20%.
[0000]
TABLE 4
Effects of p97 on thromboelastograph parameters
Conditions
Parameters
tPA
tPA+
a. Artificial fibrin-clot
1. G
d/sc
498 ± 7
446 ± 17
2. Lys (30)
%
6.5
31.9
3. CLT
min
54.7
30.3
b. Fibrin-clot with citrate-
treated serum
1. G
d/sc
13465 ± 1586
9560 ± 1626
2. Lys (30)
%
4.3 ± 0.7
11.8 ± 4.0
3. CLT
min
68.3 ± 1.6
49.1 ± 6.3
[0150] G (d/sc) is the maximum strength of the clot at maximum amplitude of the TEG trace.
[0151] The present findings are significant for several reasons. First, it was discovered that soluble p97, by interacting with plasminogen, enhances its activation by tPA. Furthermore, it is established that protein-protein interaction could positively regulate the activity of an enzyme by inducing a conformational change which lead to the exposure of active cryptic site. In addition, the data presented here in the radial clot lysis assay and the TEG analysis provide further evidence that soluble p97 positively regulates the tPA-dependent fibrinolysis by mainly decreasing the clot strength and time of lysis. Overall, the data indicate that soluble p97 increases the efficacy of the anti-thrombolysis agent tPA.
[0152] Second, perforation of the clot by soluble p97 without any release of fibrin fragments indicates that soluble p97 interaction with plasminogen induces a change in the fibrin-clot structure. Soluble p97 greatly facilitates the tPA action, leading to a localized and accelerated fibrinolysis.
[0153] In conclusion, the data presented herein indicates that human recombinant soluble p97 is as a switch activator of plasminogen since its interaction with plasminogen leads to an increase in the clot permeation and fibrinolysis by tPA. Thrombolysis with blood clot dissolving agent like tPA can reduced mortality in acute myocardial infraction.
Example IX
Inhibition of Angiogenesis by Melanotransferrin
[0154] During angiogenesis, cells must proliferate and migrate to finally invade the surrounding extracellular matrix (ECM). Moreover, metastasis is associated with tissue remodeling and invasion. In fact, when processing from migration to invasion, an additional complexity is added, as invasion comprises not only cell locomotion, but also the active penetration of cells into ECM.
Cell Culture
[0155] Cells were cultured under 5% CO 2 /95% air atmosphere. Ovary hamster cells expressing or not the membrane type melanotransferrin (respectively mMTf-CHO and mock-CHO cells) were cultured with Ham F12 suplemented with 1 mM HEPES and 10% of calf serum (CS).
Cell Invasion Assay
[0156] Invasion was performed with CHO transfected with membrane bound Mtf (p97) (mMtf-CHO) or with the vector only (MOCK-CHO) using Transwell filters (Costar, Corning, N.Y.: 8 μm pore size) precoated with 50 μg Matrigel (BD Bioscience). The transwell filters were assembled in 24-well plates (Falcon 3097, Fisher Scientific, Montreal, Quebec, Canada) and the lower chambers filled with 600 μL cell culture medium containing 10% calf serum with or without 100 nM soluble p97 as well as 50 nM IgG1 or L235. To study the effect of soluble p97 and L235 on cell invasion, CHO cells were harvested by trypsinization and centrifuged. 1×10 5 cells were resuspended in 200 μL cell culture medium without serum and containing or not 100 nM soluble p97 as well as 50 nM IgG1 or L235 and added into the upper chamber of each Transwell. The plates were than placed at 37° C. in 5% CO 2 /95% air for 48 hours. Cells that have invaded to the lower surface of the filters were fixed with 3.7% formaldehyde in PBS, stained with 0.1% crystal violet/20% MeOH, and count (4 random fields per filter) with Norten Eclipse digital software.
Transendothelial Invasion Assay
[0157] Mock-CHO and mMTf-CHO cells were seeded onto the <<blood brain barrier in vitro model>> at 100 000 cells/mL in presence of 5 mM Hoescht in supplemented Ham F12 medium with or without 50 nM of L235 (antibody directed against melanotranferrin). Cells were then incubated for 48 hours at 37° C. 5% CO 2 . After the incubation, cells were fixed in 3.7% formaldehyde in phosphate-buffered saline (PBS, Ca +2 /Mg +2 free) for 30 min and the plate were kept in the dark. The formaldehyde was then removed and cells that had migrated on the lower surface of the filter were then visualized with a Nikon Eclipse TE2000-U™ microscope-stage automatic thermocontrol system (Shizuoka-ken, Japan) at a 100× magnification using a Q IMAGING RETIGA™ camera, and counted with the program Northern Eclipse (Mississauga, Ontario).
[0158] As can be seen on FIG. 27 , these results suggest that endogenous membrane bound p97 stimulates CHO cell invasion. The invasion is inhibited by L235, indicating that membrane p97 participates directly in cell invasion. Moreover, recombinant soluble p97 could inhibit the invasion of these cells by competing with endogenous membrane bound p97.
[0159] In FIG. 27 , cell invasion assay were performed as described in Material and Methods. Cell invasion assay was performed in presence of 50 nM L235 ( 27 A) and 100 nM soluble p97 ( 27 B). Data represents means±SDs. ***P<0.001, *P<0.05 (Student t test).
Transendothelial Invasion on the BBB In Vitro Model
[0160] Since soluble p97 affected plasminogen activation, the inventors investigated whether soluble p97 might modulate brain invasion. Using the blood-brain barrier (BBB) in vitro model, CHO cell invasion was examined. Following a 48 hours incubation, mMTf-CHO cells expressing the membrane associated melanotransferrin show a higher invasive character through the BBB model, comparatively to control cells (mock-CHO cells). Following the addition of L235, an antibody raised against the melanotransferrin, the invasive potential of membrane bound p97 transfected cells seem to be stopped, demonstrating a important role for endogenous membrane bound melanotransferrin in mechanisms leading to cell invasion. The results are illustrated in FIG. 28 . In FIG. 28 , cells that migrated were visualized by fluorescent microscopy and counted (4 random fields per filter) with Norten Eclipse digital software as described hereinabove.
Discussion
[0161] The data clearly show that both pro-uPA and plasminogen interact with p97 and that these interactions are specific since no interaction between p97 and other proteins including tPA, PAI-1, plasmin, angiostatin, BSA, or ovalbumin could be measured. These results are the first to describe potential interactions between p97 and proteins of the uPA system.
[0162] In addition to its interaction with pro-uPA and plasminogen, p97 stimulates plasminogen activation by decreasing the K m of pro-uPA for plasminogen and by increasing the V max of the reaction. The conversion of pro-uPA to two-chain uPA occurs by proteolytic cleavage of a single peptide bond (Lys158-Ile159 in human uPA). This conversion can be catalyzed by plasmin or several other proteases such as plasma kallikrein, blood coagulation factor XIIa, cathepsin B, cathepsin L and prostate-specific antigen. In the present invention the SPR assay, the enzymatic assay and electrophoresis experiments all indicate that p97 induces a conformational change that increases pro-uPA activity without any apparent cleavage of pro-uPA. The two-state conformational model gave the best fits for the interactions of both pro-uPA and plasminogen with immobilized p97 on the BIAcore. Such good fits of experimental data to a multi-state model of interaction are an indication that a conformational change is taking place. Interestingly, the fragments of plasminogen generated by adding p97 were different from the plasminogen degradation by pro-uPA alone. These biochemical analyses further suggest that p97 could also be seen as a cofactor in uPA-dependent plasminogen activation.
[0163] The uPA/uPAR system has been involved in several pathological and physiological processes which require cell migration, such as tumor cell invasion and metastasis. Several reports showed that the uPA/uPAR system plays a key role in signal transduction as well as in regulation of melanoma cell migration and angiogenesis. As shown in the present invention, when p97 is added to both compartments of the Boyden chamber migration of HMEC-1 is inhibited by more than 50%. Thus, given the important role of plasmin, a protein like p97 which targets the formation of plasmin and acts on the migration of endothelial cells as well as of SK-MEL28 cells will thus affect angiogenesis and cancer progression. It was also observed in the present invention that the basal capacity for plasminogen activation by HMEC-1 decreased following p97 treatment. A recent study demonstrated that the expression of LDL receptor-related protein 1B (LRP1B), a new member of the LDL receptor family, lead to an accumulation of uPAR on the cell surface which event inhibits the migration of CHO cells. From these results, it was proposed that LRP1B negatively regulates uPAR regeneration and function whereas the net results of uPAR regeneration seems to depend on the relative expression of the two receptors.
[0164] Recently, it was shown that when glu-plasminogen is bound to cell surfaces, plasmin generation by plasminogen activators is markedly stimulated compared to the reaction in solution. This is a key element for cell migration where the process of “grip and go” would play an important role. The process of plasminogen activation system is regulated by two different mechanisms: 1) cell surface-binding sites which facilitate the productive catalytic interactions with plasminogen and thereby increases plasmin generation, and 2) protein inhibitors such as serpin inhibitors which restrict the activities of the proteases. In light of this, soluble p97 participates in the activation of plasminogen without being in the pericellular environment ( FIG. 29A ). The present invention also indicates that the migration and the plasminolytic activity of cells expressing p97 are inhibited by mAb L235, indicating that endogenous, membrane-bound p97 are involved in these processes which are associated with cancer and angiogenesis ( FIG. 29B ). Moreover, both the migration of HMEC-1 and the plasminolytic activity are diminished when exogenous p97 is added, indicating that soluble p97 affects the regulation of plasminogen activation at the cell surface ( FIG. 29C ). Thus, by breaking the equilibrium between soluble p97 and membrane bound p97, it is possible to affect cell migration of HMEC-1 and SK− MEL28 cells.
[0165] In conclusion, these are the first results indicating that p97 interacts with pro-uPA as well as with plasminogen and regulates the activation of plasminogen by pro-uPA. As shown in the present invention migration of HMEC-1 and SK-MEL28 cells is inhibited by mAb L235 and soluble p97, indicating that active and functional p97 participates in this process. Collectively, the results thus indicate that the balance between membrane-bound and soluble p97 could affect cell migration.
[0166] As mentioned above, these are the first data indicating that exogenous human recombinant soluble p97 have anti-angiogenic properties, by affecting the morphogenic differentiation of EC into capillary-like structures, by interfering with key proteins involved in angiogenesis and by inducing EC detachment.
[0167] Also as mentioned previously, the data presented herein indicates that human recombinant soluble p97 can be seen as a switch activator of plasminogen since its interaction with plasminogen leads to an increase in the clot permeation and fibrinolysis by tPA. Thrombolysis with blood clot dissolving agent like tPA can reduced mortality in acute myocardial infraction. However, damage can occur since the blow flow is restored by only 60% after 90 min. The results presented herein suggest that soluble p97 could increase the efficiency of the thrombolytic agent (tPA) when co-administrated. Furthermore, since the reoccluded clots are usually more resistant to tPA, soluble p97 administration could counter this adverse effect by increasing the therapeutic window of tPA. According to the American Heart Association, two million Americans suffer from atrial fibrillation, in which the two small upper chambers of the heart quiver instead of beating effectively. Blood in these quivering chambers can clot, travel and obstruct blood circulation. This phenomenon can also happen in the vein, where the clot would obstruct as well. Soluble p97 would enhance tPA effectiveness and broaden its therapeutic window. P97 has also the power to modify clot structure. Moreover, p97-containing gel could also be used to control new blood vessel growth and to reduce the need for coronary bypass surgery and provide effective treatment for a debilitating cardiovascular disease.
[0168] While the invention has been described in connection with specific embodiments thereof, it will be understood that it is capable of further modifications and this application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains and as may be applied to the essential features hereinbefore set forth, and as follows in the scope of the appended claims. | The invention relates to novel regulators of plasminogen activation and their use for regulating cell migration, plasminolysis, angiogenesis, fibrinolysis, for treating cancer and thrombo-embolic diseases such as heart stroke. Furthermore, the present invention relates to novel pharmaceutical compositions form regulating cell migration, plasminolysis, angiogenesis and for treating cancer. In particular, the present invention relates to a method of regulating the activation of plasminogen comprising contacting a solution of pro-urokinase (uPA) or tissue plasminogen activator (tPA) and plasminogen with melanotransferrin (p97) for a time sufficient to effect regulation thereof. | 2 |
REFERENCE TO PENDING PRIOR PATENT APPLICATION
[0001] This patent application claims benefit of pending prior U.S. Provisional Patent Application Ser. No. 61/529,958, filed Sep. 01, 2011 by Craig Souza for ERGO-SLING[TM] LAUNDRY BASKET (Attorney's Docket No. SOUZA-2 PROV), which patent application is hereby incorporated herein by reference.
FIELD OF THE INVENTION
[0002] This invention relates to household goods in general, and more particularly to an improved ergonomic laundry basket.
BACKGROUND OF THE INVENTION
[0003] Carrying laundry around a single family home, multi-unit dwelling or to and from a Laundromat is a common task. Many variations of conventional laundry baskets have been developed to assist with this task, yet most remain subject to several shortcomings. In particular, conventional laundry baskets can become very heavy and cumbersome to carry when loaded with laundry, and consequently are often difficult to grasp, lift and hold. Accordingly, a user must often exert a significant amount of effort to lift and hold a loaded laundry basket, and the exertion of that effort can sometimes lead to muscle strain or other bodily injury.
[0004] Accordingly, one object of the present invention is to provide a novel improved laundry basket which is easier to grasp, lift and hold so as to reduce the amount of effort required to carry a laundry basket and to reduce the chance of muscle strain or injury.
[0005] An additional problem associated with prior art laundry baskets is that they can be difficult to maneuver through doorways and other narrow spaces as a result of the design and/or configuration of the basket and the position of the handles thereon.
[0006] Looking now at FIGS. 1-4 , there are shown four conventional laundry baskets 5 . Maneuvering through a doorway while carrying conventional laundry baskets 5 presents a particular challenge for many people. The problem commonly occurs because conventional laundry baskets are typically designed with handles 10 at or near the extremities of the longest dimension 15 of the basket, which is typically configured to be substantially wider than the carrier's torso. Accordingly, a person carrying a conventional laundry basket must place his or her hands well outboard of his or her torso. In many cases, however, a doorway through which the carrier desires to pass is not wide enough to accommodate the longest dimension of the laundry basket, let alone wide enough to accommodate the conventional laundry basket and the added width of the carrier's hands and forearms that are disposed outboard of the widest dimension of the basket.
[0007] As a result, the carrier of a conventional laundry basket will often be forced to shift his or her grip on the laundry basket from his or her preferred position or will be forced to turn sideways or otherwise contort his or her body in order to pass through the doorway. Neither of these alternatives is particularly attractive, as they can cause the carrier to either drop the basket or assume a less natural carrying position leading to additional strain and potential injury. Shifting one's grip on the basket or turning sideways may also distract the carrier, which can create a potentially dangerous situation as such movements are often undertaken at a doorway in close proximity to a staircase (e.g., at a doorway to a staircase leading to a basement laundry facility).
[0008] Accordingly, another object of the invention is to provide an improved laundry basket that is more easily maneuvered from location to location, and particularly, through doorways.
SUMMARY OF THE INVENTION
[0009] These and other objects of the present invention are addressed by the provision and use of a novel ergonomic laundry basket, also sometimes called the Ergo-Sling™ laundry basket. The Ergo-Sling™ laundry basket includes specially designed handles and a contoured panel configured to rest against a user's body to allow a user to more easily lift, hold and carry the Ergo-Sling™ laundry basket. The Ergo-Sling™ laundry basket is also specially configured to make it easier for the user to navigate narrow spaces (such as doorways) making the Ergo-Sling™ laundry basket easier to maneuver and more user-friendly than conventional laundry baskets.
[0010] In one preferred form of the present invention, there is provided a basket for carrying an item, the basket comprising:
[0011] a proximal panel having a top portion and a bottom portion, a distal panel having a top portion and a bottom portion, two side panels extending between the proximal panel and the distal panel and each side panel having a top portion and a bottom portion, and a bottom panel connecting the proximal panel, distal panel and side panels together at their bottom portions;
[0012] wherein the side panels are longer than the distal panel and the proximal panel;
[0013] wherein each of the two side panels comprise a handle; and
[0014] wherein the proximal panel comprises a concave surface.
[0015] In another preferred form of the present invention, there is provided a method for carrying an item in a basket, the method comprising:
[0016] providing a basket for carrying the item, the basket comprising:
a proximal panel having a top portion and a bottom portion, a distal panel having a top portion and a bottom portion, two side panels extending between the proximal panel and the distal panel and each side panel having a top portion and a bottom portion, and a bottom panel connecting the proximal panel, distal panel and side panels together at their bottom portions; wherein the side panels are longer than the distal panel and the proximal panel;
wherein each of the two side panels comprise a handle; and wherein the proximal panel comprises a concave surface;
[0021] placing an item in the basket; and
[0022] carrying the basket.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023] These and other objects and features of the present invention will be more fully disclosed or rendered obvious by the following detailed description of the preferred embodiments of the invention, which is to be considered together with the accompanying drawings wherein like numbers refer to like parts, and further wherein:
[0024] FIG. 1 is a schematic view of a prior art laundry basket;
[0025] FIG. 2 is a schematic view of another prior art laundry basket;
[0026] FIG. 3 is a schematic view of yet another prior art laundry basket;
[0027] FIG. 4 is a schematic view of still another prior art laundry basket;
[0028] FIG. 5 is a perspective view of the novel ergonomic laundry basket of the present invention;
[0029] FIG. 6 is a side view of the novel ergonomic laundry basket of FIG. 5 ;
[0030] FIG. 7 is a detail view of an exemplary construction of a side handle of the novel ergonomic laundry basket shown in FIGS. 5 and 6 ; and
[0031] FIG. 8 is a top view of an alternate novel ergonomic laundry basket.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0032] Turning first to FIGS. 5-7 , there is shown a novel ergonomic laundry basket 105 , formed in accordance with the present invention, which invention may also be referred to as The Ergo-Sling™ laundry basket.
[0033] Laundry basket 105 generally comprises two side panels 110 , a distal panel 120 , a proximal panel 125 and a bottom panel 130 . Preferably, side panels 110 are longer than distal panel 120 and proximal panel 125 . Panels 110 , 120 , 125 and 130 are generally formed of a lightweight semi-rigid material, such as, for example, several kinds of plastics well known in the art. Panels 110 , 120 , 125 and 130 may be formed integrally with one another (e.g., through injection molding), or they may be joined with one another by methods known in the art, to form an open-top basket of the sort shown in FIGS. 5 and 8 . Side panels 110 , distal panel 120 and proximal panel 125 typically meet their adjoining panels at approximately a right angle, and the angle may be rounded on its inside and outside edges. Side panels 110 , distal panel 120 and proximal panel 125 generally extend upwardly from bottom panel 130 and may meet bottom panel 130 at approximately a right angle, or at an angle slightly greater than ninety degrees such that the perimeter of basket 105 measured at the top edges (discussed in greater detail below) is greater than the perimeter of the bottom panel 130 .
[0034] Side panels 110 are approximately rectangular in shape but may have a slightly trapezoidal shape if the perimeter of basket 105 measured at the top edges is greater than that of the bottom panel 130 , as discussed above. Side panels 110 may comprise one or more perforations 135 , or may be formed without perforations. The top portion of side panels 110 may be formed with top edges 140 .
[0035] Ergonomic laundry basket 105 further comprises at least two handles 160 formed along the top of side panels 110 . Handles 160 are either formed integrally with top edges 140 or may be joined to top edges 140 by ways known in the art. Significantly, handles 160 are configured such that the distal ends 170 of handles 160 are further removed from top edges 140 than the proximal ends 180 of handles 160 . In one preferred form of the invention, distal ends 170 of the handles are removed from top edges 140 by vertical risers 171 so as to set the slope of the handles at approximately 30 degrees (see FIG. 7 ). Handles 160 may also be covered from their distal ends 170 to their proximal ends 180 by a cushioned non-slip covering 190 . Cushioned non-slip covering 190 may be formed of foam, memory foam or other materials known in the art. In one preferred form of the invention, the length of handles 160 from their distal ends 170 to their proximal ends 180 is approximately six inches.
[0036] In one embodiment, top edges 140 may also be formed with depressions 150 under handles 160 , so that it is easier for a user to grip handles 160 , as will be discussed in further detail below.
[0037] Distal panel 120 may be formed with a top edge 200 similar to that of top edges 140 .
[0038] Distal panel 120 may also be provided with a handle 205 . Handle 205 is either formed integrally with top edge 200 or may be joined to top edge 200 by ways known in the art. Handle 205 may also be covered with a cushioned non-slip covering 210 similar to that of cushioned non-slip coverings 190 .
[0039] Proximal panel 125 may be formed with a concave surface 215 , which may “hug” the user's hips, waist or abdominal area when the user is carrying ergonomic laundry basket 105 . Top portion of proximal panel 125 may be formed with an edge 220 similar to that of top edges 140 of side panels 110 and top edge 200 of distal panel 120 . Top edge 220 may also be covered with a cushioned non-slip covering 225 similar to that of cushioned non-slip coverings 190 and 210 .
[0040] Preferably, top edges 140 , top edge 200 and top edge 220 are formed integral with one another.
[0041] As previously described, basket 105 also features concave panel 215 on proximal panel 125 . Concave panel 215 allows the user to more comfortably carry the basket against the user's body, thereby further distributing the weight of ergonomic laundry basket 105 and the items placed therein. Concave panel 215 may also be fitted with friction-enhancing “gripping strips” (not shown) to lessen the likelihood of ergonomic basket 105 sliding along the user's torso and to increase safety. The increased friction offered by such “gripping strips” serves to reduce the load on user's arms and wrists.
[0042] In another embodiment, and looking now at FIG. 8 , distal panel 120 may be formed with a convex surface 201 which extends distally from bottom panel 130 . Convex surface 201 provides additional space within basket 105 .
[0043] To lift and carry laundry basket 105 , a user may position himself or herself such that the user is facing concave surface 215 of proximal panel 125 . User then grasps handles 160 at the tops of side panels 110 and lifts basket 105 such that cushioned non-slip covering 225 on top edge 220 is resting against the user's hips, waist or abdomen.
[0044] In some circumstances, a user may find it useful to carry ergonomic laundry basket 105 with only one hand, allowing the other hand to remain free for accomplishing tasks such as opening or closing doors or switching lights on or off. In this circumstance, a user may carry ergonomic laundry basket 105 with one hand by lifting the basket in the manner disclosed above, placing concave surface 215 against the user's waist, hips and/or abdomen and, while holding concave surface 215 against the user, shifting one hand from handles 160 to handle 205 .
[0045] The position of handles 160 on top edges 140 , and the configuration of handles 160 , is a significant advance over the prior art. By angling handles 160 such that distal ends 170 are removed from top edges 140 , a user's wrists are allowed to remain in a more natural and less stressful position when gripping handles 160 than they otherwise would be if the user was gripping handles 10 of conventional laundry baskets 5 which are not so configured.
[0046] Furthermore, by forming handles 160 at an angle, handles 160 also allow a user to transfer some of the weight of the basket and its contents from the arms and wrists of the user to the rest of the body (e.g., to the hips, waist and/or abdomen), via the contact between user and cushioned non-slip covering 225 and concave panel surface 215 . These elements cooperate to offer increased comfort for the user. In addition, handles 160 are also covered with cushioned non-slip covering 190 that allow a user to maintain a firm and comfortable grip on handles 160 , which are also sized so as to make it easier for a user to grip and hold.
[0047] Thus, laundry basket 105 is an ergonomic laundry basket that makes it easier for a user to grasp, lift and hold the basket so as to reduce the amount of effort required to carry a laundry basket and to reduce the chances of muscle strain or injury.
[0048] Additionally, laundry basket 105 is an ergonomic laundry basket that makes it easier to maneuver from location to location, and particularly through doorways.
[0049] Laundry basket 105 is configured to be carried such that side panels 110 of ergonomic basket 105 extend distally in front of the user. This is a significant improvement over prior art laundry baskets, which are configured to have the longest dimension (e.g., longest dimensions 15 of conventional baskets 5 ) extending laterally across the user's torso and approximately perpendicular to the user's direction of travel when carrying the basket.
[0050] Significantly, by configuring ergonomic basket 105 to have handles 160 at the tops of side panels 110 which extend distally in front of the user while concave surface 215 of proximal panel 125 rests against the user, the user is able to keep his or her arms and hands closer to one another while carrying ergonomic basket 105 than he or she would otherwise be able to if carrying conventional laundry baskets 5 of FIGS. 1-4 . This feature reduces the overall carrying width (i.e., the width of the basket plus the width of user's hands and/or forearms) of the ergonomic basket 105 , thus making it easier for the user to maneuver. In particular, this feature of laundry basket 105 makes it significantly easier for a user to pass through doorways while carrying laundry basket 105 and without having to shift his or her grip from the preferred position or be forced to turn sideways or otherwise contort his or her body in order to pass through the doorway.
Modifications Of The Preferred Embodiments
[0051] It will be understood that many additional changes in the details, materials, steps and arrangements of parts, which have been herein described and illustrated in order to explain the nature of the invention, may be made by those skilled in the art while remaining within the principles and scope of the present invention. | A basket for carrying an item, the basket comprising:
a proximal panel having a top portion and a bottom portion, a distal panel having a top portion and a bottom portion, two side panels extending between the proximal panel and the distal panel and each side panel having a top portion and a bottom portion, and a bottom panel connecting the proximal panel, distal panel and side panels together at their bottom portions; wherein the side panels are longer than the distal panel and the proximal panel; wherein each of the two side panels comprise a handle; and wherein the proximal panel comprises a concave surface. | 3 |
CROSS-REFERNCE TO RELATED APPLICATIONS
[0001] Not Applicable
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] Not Applicable
REFERENCE TO SEQUENCE LISTING, A TABLE, OR A COMPUTER PROGRAM LISTING COMPACT DISK APPENDIX
[0003] Not Applicable
BACKGROUND OF INVENTION
[0004] 1. Field of the Invention
[0005] The field of invention to which this invention relates is the collection of animal solid waste. More specifically, this invention constitutes a device or system that integrates into common leashing systems and will be used by dog owners to clean up their dog's solid waste material while walking their dog. The design of this invention allows the pet owner to easily and quickly pick up the waste material, contain it in a sanitary, inexpensive, disposable bio-degradable container to carry the waste and discretely transport it, without having to carry an additional device in ones free hand, or further encumbering the leash hand, until it can be disposed of properly. Other products or prior art provide ways to carry plastic bags conveniently before use or in other cases provide a means to make “collecting” the waste material easier but none provide the pre-use convenience, speed, and a means to carry the waste after collection with out using ones free hand (non leash hand) or without further encumbering the leash hand in a discrete manner until disposal.
[0006] This invention, allows the dog owner to pick up the waste more quickly than other products usually less than 5 seconds start to finish, the owner does not have to make tactile connection with the waste, nor will the waste make contact with non-disposable areas of the devise, the disposable liner is biodegradable, and the waste is contained discretely within the device which is part of the leash system thereby alleviating the need to carry the waste in ones free hand or further encumber the hand holding the leash.
[0007] With 45 million dog owners and 65 million dogs in the United States alone, cleaning up dog waste can be a major problem in many urban and suburban areas in the U.S. and other cities around the world. Today in many cities it is mandatory, in others it is requested. In all cases, the easier and less offensive the process of waste pick up is, the more people will act responsibly in cleaning up after their pet in an environmentally friendly way.
[0008] 2. Description of Prior Art
[0009] The following patents illustrate various prior art devices and methods of collecting pet waste:
[0010] U.S. Pat. No. 6,554,335 describes a pet waste collection system, which includes a main housing having a hollow inside and having a top, a bottom, a front, and a back and at least one sidewall, and having an opening accessible to the hollow inside area. There is also a telescopically extendable and contractible pole attached at a first end to the hollow inside area of the main housing and attached to a collapsible frame at its second end. The collapsible frame unfolds for a waste receptacle, i.e. a “pooper” bag, and is spaced behind the pet during defecation. In some embodiments, an attachment hook is located on said main housing for attachment thereof to a leash, a belt, or other attachable area or item.
[0011] U.S. Pat. No. 2,141,007 describes a shovel comprising walls forming an enclosure open at one end and closed at the opposite end, a sleeve rigid with the closed end of the shovel angularly and rearwardly therefrom, a pair of longitudinally spaced flanges integral with said sleeve, a collar rotatably mounted around the sleeve between said flanges and held from longitudinal movement thereby, a handle extending into and rigidly attached to said sleeve and projecting upwardly and rearwardly therefrom, and a rotary sleeve mounted on the outer end of said handle approximately at right angles to said first named sleeve and facilitating turning of the shovel to extend the open end thereof downwardly and discharge the contents therefrom.
[0012] U.S. Pat. No. 3,052,214 describes a disposable catcher for trapping and containing excrement and the like for disposal thereof, said catcher comprising, in combination, a bag holding and operating means comprising a stick, said stick comprising connecting rod and a connecting tubular rod holder disposed therearound to limit movement of said rod between a forward lid open and a rearward lid closed position, and a disposable bag readily detachably connected to said stick, said bag comprising a disposable bag body and a movable lid, said lid being readily detachably connected to said connecting rod and said bag body being detachably connected in supporting position to said connecting rod holder, whereby said lid can be moved to open and closed positions by movement of said connecting rod, said bag being readily detached from said stick by detachment of said lid and said bag body from said connecting rod and connecting rod holder, respectively.
[0013] U.S. Pat. No. 3,139,299 describes a refuse collector, comprising in combination: an elongated and vertically extending tube element, said tube having an outlet at the bottom thereof; an elongated element in longitudinal sliding in relationship and by the tube element, one of said elements being rigid and having a handle section for manipulating the collector; a bowl carried by and at the lower end of one of said elements; a scoop for the bowl; means for pivotally connecting the scoop to both of said elements; means coupling the upper end of the tube with a source of fluid; and a manually actuated valve carried by the tube for controlling the flow of liquid through the tube.
[0014] U.S. Pat. No. 3,281,178 describes a device for collecting and disposing of animal fecal matter, comprising, in combination, a handle, a first frame element, a second frame element, one end portion of said first frame element being spaced apart from and oppositely positioned with respect to one end portion of said second frame element, the other end portion of said first frame element being connected to said second frame element, said handle member being transversely positioned with respect to both said first frame element and second frame element and being connected to said connected first and second frame elements, and a bag member removably attached to said connected first and second frame elements at their respective one end portions spaced apart from and oppositely positioned with respect to each other, said bag member having a collar and a body portion integral with said collar, said collar being sealed to said body portion at least two opposite points thereof, each of said two opposite points being between said two spaced apart and oppositely positioned end portions of said first and second frame elements, said collar being positioned over said two spaced apart and oppositely positioned end portions of said first and second frame elements, said body portion being positioned between said first and second frame elements, whereby said device can be easily used without any fecal matter to be collected contacting the frame elements and whereby said bag member can be easily removed and then closed and sealed by raising and inverting one side of said collar.
[0015] U.S. Pat. No. 3,286,826 describes a portable combination flat package for use in removing dog refuse from an area in which it is deposited including: a flexible fibrous container in the form of a sack having an open end that is defined by first and second flat side walls, two end walls and a bottom, with said end walls and bottom having centrally disposed fold lines formed therein that extend the length thereof, and said first side wall includes as an integral part thereof an extension that projects beyond said open end, which container is selectively disposable in either a first position in which it is flattened, a second positioned in which it is expanded to receive dog refuse through said open end when said extension is placed in contact with the surface on which said refuse rests, and a third position in which said container is rolled upon itself with said refuse within the confines thereof, with said extension when said container is in said third position being wrapped thereabout to seal the same; a rectangular sheet of cardboard of substantial stiffness disposed within said container when in said first position to prevent lateral creasing of said container, which sheet has a plurality of spaced fold lines formed therein that extend longitudinally and transversely therein which aid in shaping said sheet into a scoop when said sheet is removed from said container, and when said sheet is so shaped it defines two parallel longitudinally extending flanged that act as stiffeners, in the use of said scoop to pick up refuse and deposit the same together with said sheet in said container when in said second position; and, tie means within said container in said third position for holding said container in said third position with said refuse and sheet within the confines thereof with said extension being wrapped around said container to seal the same.
[0016] U.S. Pat. No. 3,431,008 describes a portable scavenging apparatus for removing feces of animals and other untouchable objects comprising a box having an opening therein and a lid adapted to selectively close and open said opening, a stick having a first end mounted to a wall of said box, means for moving said lid selectively between its closed and open positions including a lever, a link, an arm, and a spring, said lever being pivotally mounted at a predetermined point intermediate its ends to said stick at a predetermined point adjacent the second end of said stick, a handle mounted in fixed position to said stick to provide a stationary member toward which one end of said lever may be manually pivoted, said spring being interposed between said handle and said lever to normally urge said one end of said lever away from said handle, said link being attached to the opposite end of said lever so as not to be moved away from said handle when said lever is manually pivoted toward said handle, said link being mounted to said arm and said arm being operative when said lever and said link are moved to move said lid between its closed and open positions.
[0017] U.S. Pat. No. 3,446,525 describes in a portable pickup device for grasping and transporting unclean material such as animal droppings and the like, said device having an elongated body provided with a handle at one end: pickup means carried at the other end of the body including a pair of pickup members in virtually parallel planes, said pair of pickup members including parallel bottom straight portions cooperable to move along a surface in close relation thereto whereby at least one straight portion is adapted to move beneath a dropping to be picked up, at least one of said pickup members being an open frame; means for moving at least one of the pickup members to and away from the other; and a disposable compliant wrapping means received and held on said pickup means with an opening at said bottom portions, the open frame pickup member being adapted to permit outward lateral displacement of said compliant wrapping means when a dropping is lifted by said straight portions of the pickup means for containing the dropping in said wrapping means at one side of the pickup means.
[0018] U.S. Pat. No. 3,560,039 describes an apparatus for handling and disposing of animal excrement and the like comprising in combination a tong member including a pair of levers pivotally connected together intermediate their ends, loop handle portions at one end of each of said levers, the other end of each of said levers having a transverse elongated scoop portion which curves concavely inwardly toward the opposite lever whereby said scoop portions form a closed-end scoop when said long end member is in the closed position, and tissue-retaining means on said tong member for retaining a package of tissues therein, said tissue retaining means including a receptacle connected to one of said pair of levers and a removable cover on said receptacle having an opening therein for the removal of tissues from said receptacle.
[0019] U.S. Pat. No. 3,606,436 describes a portable device for picking up objects underfoot comprising: a first assemblage including a first blade-like member secured to the lower end of a first operating rod and projecting angularly therefrom; a second assemblage including a second blade-like member secured to the lower end of a second operating rod and projecting angularly therefrom; hinging means pivotally interconnecting said first and second assemblages for pincers-like movement of said blade-like members upon manipulation of said operating rods; and, a bag having a portion of its open end detachably secured to said first blade-like member, another portion of its open end detachably secured to said second blade-like member, and a portion of its closed end detachably secured to one of said operating rods so that the inverted bag is selectively opened and closed by the pinchers-like movement of said blade-like members resulting from manipulation of said operating rods.
[0020] U.S. Pat. No. 3,659,891 describes a refuse collecting device having an improved tubular bag-mounting member at the lower end of a handle for collecting refuse such as animal leavings and the like. The refuse is collected in a disposable bag removably mounted on the tubular element in an improved manner for positive association with the tubular element during use while yet providing for facilitated withdrawal of the bagged matter in a sanitary manner.
[0021] U.S. Pat. No. 3,676,887 describes a flexible bag body portion that has a substantially rigid blade element permanently attached to one side wall thereof adjacent the open mouth of the bag body portion. A flexible closure flap is carried by the opposite side wall of the bag body portion and has an adhesive sealing area coact with a like area on the side wall of the body portion carrying the blade element. The bag is sealed with the litter and the blade element therein prior to disposal.
[0022] U.S. Pat. No. 3,716,263 describes a device for collecting articles and substances, comprising in combination: a handle; an adjustable shaft surmounted by said handle; a pair of outwardly inclined arms depending from said adjustable shaft; pivotal means depending from said arms; said pivotal means being normally maintained in an inclined, open position by spring means depending from said arms; said pivotable means being disposable into a horizontal, closed position when said pivotable means are in abutment with a surface and said handle is depressed; descendable means depending from said arms and contactable with said pivotable means when it is in said closed position, thereby obstructing the return of said pivotable means from said closed to said open position.
[0023] U.S. Pat. No. 3,757,737 describes a mechanical device for sequentially loading multiple bodies of animal dropping from the ground in to a disposable bag. The illustrated device has an elongated handle which carries a pickup means at its lower end. The pickup means includes means for releasably holding a bag with the mouth of the bag held open in a generally vertical plane, and a movable paddle proportioned and arranged to engage and propel a body of animal droppings into the bag through the open mouth. The movement of the paddle is remotely controlled from the upper end of the handle by a manually movable lever which is operable to impart a rapid propelling movement to the paddle.
[0024] U.S. Pat. No. 3,778,097 describes a device for retrieving litter that has manually actuated positioning means connected to a litter receptacle holder and a pushing member adapted to be enclosed in an envelope releasably secured about the pushing member. Actuation of the positioning means causes coaction between a litter receptacle mounted in the litter receptacle holder and the enveloped pushing member, so that litter is forced into the litter receptacle and held in the litter receptacle by the pushing surface. While the litter is being held within the litter receptacle by the enveloped pushing member, the envelope is released from about the pushing member and reversed to envelope the opening of the litter receptacle. The litter receptacle can then be manually ejected into the envelope when the positioning means are actuated to move the pushing member away from the litter receptacle.
[0025] U.S. Pat. No. 3,786,780 describes a portable canine toilet, in combination a holder and disposable waste receiving means adapted to be removably fitted upon the holder. The holder has a projecting means mounted on its rod portion, and the receiving means has a partially circumferential sleeve along its upper portion and into which the lower part of the holder is inserted. The receiving means also has a stringed collar at the top of the upper portion, the protruding portion of the string normally positioned on the projecting means.
[0026] U.S. Pat. No. 3,804,448 describes an elongated light weight shaft that has at one end a handgrip portion and at the other end a scavenging scoop receptacle with an inlet opening facing transversely of the length of the shaft. An electric light on or near the handgrip portion illuminates the receptacle inlet and the locale adjacent thereto. The implement may be manipulated by one hand of a user while the user is standing in his normal upright position. The scoop receptacle may include, or support, a detachable disposable container or liner. A closure lid is hingedly mounted relative to the scoop receptacle so that the lid can be moved into an open position while the receptacle is in scooping position and into closed position upon completion of the scooping operation, selectively, by manipulation of the shaft by the supporting hand of user. A pusher tool or brush is carried by the shaft near the receptacle. Propelling means are provided in the receptacle and are operable manually to propel the material scooped into the entry of the receptacle farther into the receptacle and away from the inlet opening so that the material can be carried in the receptacle without danger of spillage even with the shaft carried substantially upright.
[0027] U.S. Pat. No. 3,819,220 describes a sanitary device for pets which comprises a wand having at one end a pair of spring arms which normally are biased apart. A disposable receptacle having sleeve portions around its normally open top has such portions fitted on said arms to be held open thereby and positioned beneath a pet to receive feces as the latter is discharged. The receptacle is fitted on the arms; the arms squeezed together, the receptacle wrapped around the arms and a sleeve telescoped on the wand to retain the device in readiness. After use, the receptacle may be expelled from the arms by extending the sleeve.
[0028] U.S. Pat. No. 4,019,768 describes a device for sanitary pickup of ground deposited excrement comprises a metal frame structure having an excrement engaging pickup portion and a conventional bag supporting portion. Said bag holding portion positively retains a conventional shopping bag on the holding portion in a manner to hold the mouth of the bag open for ready reception of the said excrement together with additional structure supported by the handle for quick and easy release of said bag from positive retention on the support portion. Additional covers are also provided for the excrement engaging portion of the device to increase the usefulness of said device.
[0029] U.S. Pat. No. 4,215,887 describes a pickup device of highly functional yet inexpensive construction, comprising a pair of loop-shaped portions that are hinged together, with the loop-shaped portions being movable to a widely separated position such that an inverted bag that has been partially turned inside out may be inserted between the loops. Handle portions located above the hinge locations are able to be grasped by the user and brought together, with such action serving to bring base portions of the loops, as well as certain neck portions of the bag together. This action makes the device readily adaptable for the picking up of material from a floor or sidewalk, such as that deposited by an animal, with this arrangement advantageously serving to cause the removed material to be enveloped in the bottom portion of the bag, with the upper portions of the bag thereafter being easily brought together and tied, and with the exterior of the bag and the pickup device remaining unsoiled throughout the entire procedure.
[0030] U.S. Pat. No. 4,323,272 describes a hand portable and single hand operable device for picking up animal excrement and the like comprised of a pair of metal rods fixed close enough together at one end as V shaped extensions from a spring loop to form a handle portion for grasping with one hand about both rods which are deflectable toward each other by pressure of the hand. At the other end of each of the rods is a bag support member comprised of an elongated bag support wire loop formation having two substantially parallel width portions and two opposed length portions with length portions farthest from the handle portion in each bag support loop formation being straight and parallel to each other and moveable toward each other into line contact with each other by deflection of the rods. A bag having flexible sidewalls and an opening with a cuff is mounted on the respective bag support wire loop formation in a manner that the opening is at and controlled by the parallel straight portions of the bag support loop formations.
[0031] U.S. Pat. No. 4,341,410 describes a frame that comprises a handle and a pair of legs extending therefrom with the handle being substantially U-shaped and having a taut wire spanning the distal ends of the legs. A plastic or paper bag is engaged between the legs with one side of the open end folded over the taut wire and the legs and the forefinger of the hand holding the handle engaging the other side of the open end and tensioning the same against the wire. This holds the bag in the open position. The primary use is for scooping up waste material from animals such as dogs but it can also be used to hold a bag upright in the open position with one hand so that the bag can be filled with material by the other hand. It can also be used in industry for sanitary sampling of granular, comminuted, or liquid materials. In one embodiment the frame is foldable for easy storage.
[0032] U.S. Pat. No. 6,039,370 describes a portable pet toilet having an elongated pole having first and second ends. The first end provides a handle. Securely mounted on the second end of the pole is a pair of selectively adjustable arms for supporting a disposable receptacle. The arms are adjustable in order to provide the capability of accommodating receptacles of different sizes and shape.
[0033] Notwithstanding the prior art, the present invention is neither taught nor rendered obvious thereby.
BRIEF SUMMARY OF THE INVENTION
[0034] The Scoopeeze© Portable Canine Waste pick-up device consists of 4 parts, 1.) The detachable Handle 2.) The Outer semi-circle 3.) The Inner semi-circle insert(s) inserts 4.) The liner with extended flap
[0035] Scoopeeze© Portable Canine Waste pick-up device is made of one plastic, Nylon, or other synthetic materials, outer semi-circle and one or two polypropolene concentric inner semi-circular inserts, and disposable, opaque, bio-degradeable plastic, or other synthetic or composite material liners, and a detachable positive connect handle that provide a highly portable, clean, non tactile way to pick up canine waste while on a walk with a dog.
[0036] The Scoopeeze© Portable Canine Waste pick-up device integrates its form and function with traditional leashes by utilizing a metal clip through the eyelet in the handle or with commonly used retractable leashes by removing the handle and connecting the retractable leash to the docking feature on the outer semi-circle of Scoopeeze©.
[0037] The problems associated with other means of picking up canine waste material are that they are awkward to prepare for use, or they require the pet owner to use their hand to pick up the waste, or they require the pet owner to carry a bag of waste exposed to the public until they find a suitable trash recepticle, or they require carrying an additional device not integrated into the pet leashing system.
[0038] By it's design Scoopeeze© allows the pet owner to very quickly, usually less than 5 seconds, prepare, contain and cover solid dog waste in an opaque biodegradable disposable container which remains out of sight as part of the leash system, requiring only one hand, until a suitable trash receptacle is located.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
[0039] FIG. 1A Scoopeeze© Portable Canine Waste Pick Up Device entire system
[0040] FIG. 2A Scoopeeze© Portable Canine Waste Pick Up Device in waste collected mode with flexible sheet sealed over waste.
[0041] FIG. 3A Scoopeeze© Portable Canine Waste Pick Up Device docked with retractable leash.
[0042] FIG. 4A Scoopeeze© Portable Canine Waste Pick Up Device detachable handle with eyelet for metal ring.
[0043] FIG. 5A Scoopeeze© Portable Canine Waste Pick Up Device inner semi-circle insert
[0044] FIG. 6A Scoopeeze© Portable Canine Waste Pick Up Device liner and flexible sheet.
[0045] FIG. 7A Scoopeeze© Portable Canine Waste Pick Up Device detachable handle docked with outer semi-circle.
DETAILED DESCRIPTION OF THE INVENTION
[0046] The Scoopeeze© Portable Canine Waste pick-up device consists arts: 1.) The detachable handle made by injection molding ABS or 2.) The Outer semi-circle made by injection molding ABS or Nylon. 3.) The Inner semi-circle insert(s) inserts made by injection molding polypropylene or other synthetics. 4.) The liner made by vacuum forming bio-degradable plastic or other bio-degradable material.
[0047] Scoopeeze© Portable Canine Waste pick-up device is made of one plastic, Nylon, or other synthetic materials, outer semi-circle and one or more concentric inner semi-circular inserts disposable, bio-degradeable plastic, or other synthetic or composite material liners, and a detachable positive connect handle that provide a highly portable, clean, non tactile, discrete way to pick up canine waste while on a walk with a dog.
[0048] The Scoopeeze© Portable Canine Waste pick-up device integrates its form and function with traditional leashes by utilizing a metal clip through the eyelet in the handle or with commonly used retractable leashes by removing the handle and connecting the retractable leash to the docking feature on the outer semi-circle.
[0049] The outer semi-circle is made of a heavy gauge, approximately ⅛-¼ inch thick, plastic, Nylon, or composite, or other synthetic material that forms approximately a 315 degree concave arc that is open on both ends. The diameter of the arc and the width of the “SCOOPEEZE”© elements (outer semi-circle, inner semi-circle insert inserts and liners) change for small, medium, or large size dogs. The approximate sizes are:
Small Dia = 3 inches Width = 3 inches Medium Dia = 4 inches Width = 4 inches Large Dia = 7 inches Width = 7 inches
[0050] The outer semi-circle has a detachable handle that attaches to the upper area of the outer semi-circle. The detachable handle contains an eyelet at the forward end that allows a metal ring for attaching the handle of a normal non-retracting leash. When attached to a standard leash the detachable handle provides a more comfortable and solid griping surface. When the detachable handle is removed it reveals that the outer semi-circle of “Scoopeeze”© has a molded docking unit which allows the connection of any third party retractable leash to the upper area of the “Scoopeeze”© device.
[0051] The inner semi-circle insert insert is made of polypropylene, plastic or composite or other synthetic material. The size and arc conform to the inner diameter and width of the outer semi-circle. The inner semi-circle insert covers 180 degrees. In addition, the inner semi-circle insert is closed on both ends. One of the ends has an elliptically shaped protrusion, or tab which facilitates the manual rotation of the inner semi-circle insert insert.
[0052] The leading edge of the inner semi-circle insert is beveled to create a thin scooping edge to easily lift and move under the waste material. A groove is located in the outer circumference of the leading and trailing edges of the inner semi-circle insert to facilitate the positive connection of the liner.
[0053] The liner is a thin semi ridged plastic, composite, synthetic or organic biodegradable material that has the same general shape as the inner-semi circle and conforms to the contour of the inner circumferance of the inner semi-circle insert insert. The liner has a lip on all four edges that wraps and covers the edges of the inner semi-circle insert insert. The liner snaps into place by way of a slight groove located in the outer circumference of the leading and trailing edges of the inner semi-circle insert.
[0054] Attached to the trailing edge of the liner is a very thin very flexible sheet of bio-degradable plastic, composite, synthetic, or organic material which when the inner semi-circle insert insert is turned, forms a cover over the open area of the inner semi-circle insert and liner and encloses the waste material as the inner semi-circle insert is turned. The leading edge of the liner is coated with a light adhesive that comes into contact with the flexible sheet as the inner semi circle is rotated This thin plastic sheet also keeps waste material from coming into contact with the outer semi-circle, and the inner semi-circle insert.
[0055] The detachable handle, outer semi-circle, inner semi-circle insert and inner semi-circle insert liners will be available in many colors.
[0056] Operation: two methods of operation: If the waste material is contained in a “pile” the “Scoopeeze”© with a liner in position is placed over the waste material with the inner semi-circle insert insert in the up position or ready position within the outer semi-circle. The thin flexible sheet material trailing from the liner is positioned to the rear of the outer semi-circle. This allows the open area of the outer semi-circle to pass over the waste material. When the outer semi-circle is touching the ground the pet owner manually rotates the tab on the sidewall of the inner semi-circle insert insert in a clockwise direction.
[0057] As the front edge of the inner semi-circle insert scoops under the waste material the flexible sheet material begins to seal the waste material within the liner in the inner semi-circle insert insert. When the inner semi-circle insert insert has been rotated 180 degrees the waste is contained and sealed within the inner semi-circle insert insert. The “Scoopeeze”© will carry the waste material discretely sealed until a suitable trash or waste receptacle is reached. Then the inner semi-circle insert insert is manually slid laterally out of the outer semi-circle and the liner containing the waste material is disposed of. A new liner is placed into the linner semi-circle insert insert, the inner semi-circle insert insert and liner are then placed into the outer semi-circle. The “Scoopeeze”© is now ready for another use.
[0058] The second method of operation is like the first except for the following: If the waste material is not piled, but rather, spread out in a random fashion, the inner semi-circle insert insert and liner are removed from the outer semi-circle. The pet owner uses the inner semi-circle insert and liner to move the waste material into a pile. The inner semi-circle insert is then laid concave side down over the waste with the flexible sheet material component of the liner to the rear and flat on the ground. The “Scoopeeze”© outer semi-circle is then brought in behind the inner semi-circle insert. The pet owner slightly lifts the rear of the inner semi-circle insert and as the outer semi-circle is slid under the inner semi-circle insert, then rotates clockwise the protruding tab on the inner semi-circle insert. As the inner semi-circle insert is rotated it starts to seal the liner and when the inner semi-circle insert has rotated 180 degrees the waste is sealed in the disposable liner and the inner semi-circle insert is back in the outer semi-circle. The waste is discretely sealed and ready to be disposed of properly.
[0059] Left or Right hand operation: By placing the elliptical protrusion or tab on the inner semi-circle insert on the right hand side of the outer semi-circle, the “Scoopeeze”© is ergonomically designed for a right-handed person. For left-handed people the inner semi-circle insert is loaded so the protrusion or tab is on the left side of the outer semi-circle.
[0060] Configurations: Using “Scoopeeze”© with retractable or standard leashes, Configuration one: Attached to a pre-existing retractable leash: With the “Scoopeeze”© detachable handle removed, the top area of the outer semi-circle has a molded docking area which allows the lower portion of any 3 rd party retractable leash to be connected to the “Scoopeeze”© device. Connections between the “Scoopeeze”© and the retractable leash are made by industrial strength Velcro strips placed within the contours of the outer surfaces of the “Scoopeeze”© docking area and the lower portion of the retractable leash. The converging angles of the docking area also squeeze the retractable leash as it is placed into the Scoopeeze© dock.
[0061] Configuration Two: Attached to a traditional leather, nylon or other material leash. In this configuration, the Detachable handle is docked to the outer semi-circle. The eyelet at the front end of the Detachable handle holds a metal ring. The metal ring is used to connect to the handle part of a standard leash to the Detachable handle. This configuration provides a more ergonomic handle by which to control the pet and when docked with Scoopeeze© operates as described above.
[0062] Scoopeeze is unique in that prior technology in this field fails to address one or more of the following problems. Time, touch, portability, esthetics.
[0063] The simplest form of waste pick up while walking a dog is to invert a plastic bag over ones hand and pick up the waste while using the other hand to pull bag to cover waste. Some devices have been manufactured to dispense the plastic bags and attach to a common leash. Other products have been designed to facilitate pushing the waste into a manufactured opening attached to a plastic bag or into a cardboard container. One or more of these problems exist with these technologies: they take to much time to prepare, the pet owner is obliged to grasp the waste material, the waste material once contained must be carried in ones free hand, or encumber the leash hand. Further, Scoopeeze© in very efficient with resources as it uses a minimum of disposable material whereas other products tend to be completely disposable Scoopeeze addresses all of the above problems in that it's preparation for use and time to pick up waste material is extremely short, the pet owner never has to use their hands to grasp the waste material, the waste container is neatly contained within the Scoopeeze housing so it is out of sight, the Scoopeeze device is integrated into the leash system so the waste is not carried by the free hand nor is it carried separately by the leash hand.
[0064] The device efficiently uses material resources, and the contours and vibrant colors of this device make it an esthetically pleasing addition to dog walking equipment. | The device called Scoopeeze™ is a portable canine waste pick up device uniquely designed to aid pet owners while walking their dog. Consisting of two interrelating nylon, polypropylene or other plastic semi-circles and a biodegradable sanitary lining. The Scoopeeze™ device allows the dog owner to pick up canine waste far more quickly than standard means, contain the waste without “touching” or grasping the waste, discretely carry waste until proper disposal, provides an esthetically pleasing and elegant way to achieve the above. When used in combination with a standard leash, the Scoopeeze™ handle provides a more ergonomic and stronger means of pet control. When used with retractable leashes the handle is removed, the Scoopeeze™ is “docked” and the same unique, fast, sanitary, and elegant features are available to the pet owner. | 4 |
TECHNICAL FIELD
[0001] This invention relates to an ultraviolet (UV) absorber composition containing a specific triazine compound and a specific phosphite compound and/or hindered phenol compound and a synthetic resin composition containing the same. More particular, the invention relates to a UV absorber composition and a synthetic resin composition which are useful in applications to optical materials, such as optical films and optical sheets, including those used in liquid crystal displays (LCDs), such as a protective film or sheet for a polarizing plate, a retardation film, a viewing angle compensation film, an antiglare film, a luminance-improving film, a diffuser film or sheet, a lens film or sheet, an antifog film, an antistatic film, and a light guide film; various substrates; various functional films used in plasma displays, such as an antireflection film; and various functional films used in organic electroluminescence (EL) displays.
BACKGROUND ART
[0002] It is known that synthetic resins, such as polyethylene, polypropylene, styrene resins, polyvinyl chloride, and polycarbonate, and organic pigments and dyes undergo deterioration, such as discoloration and reduction in mechanical strength, by the action of light so that they do not withstand long term use.
[0003] To protect these organic materials from deterioration or control the wavelengths of transmitted light, a variety of UV absorbers have hitherto been used. Known UV absorbers include benzophenone compounds, benzotriazole compounds, 2,4,6-triaryltriazine compounds, and cyanoacrylate compounds.
[0004] For example, patent literature 1 below discloses a technique of using a UV absorber, such as a benzotriazole compound or a triazine compound, in applications to optical materials. Patent literature 2 below reports a norbornene resin film containing a UV absorber.
[0005] However, the conventional UV absorber bleeds out or causes color change when added in an amount providing sufficient absorption required in optical applications.
[0006] Patent literature 3 below discloses a triazine compound, which is used in the present invention, as a UV absorber excellent in resistance to weather and heat. The compound is also reported in patent literature 4 below as a UV absorber that exhibits UV absorption suited for applications to optical films and hardly bleeds out.
[0007] Although the triazine UV absorber hardly bleeds out, exhibits UV absorption suited for applications to optical materials, and imparts resistance to thermal deterioration to synthetic resins, it has the problem of poor resistance to thermal coloration, that is, it is susceptible to coloration during, for example, high-temperature molding of synthetic resins in which it is incorporated.
CITATION LIST
Patent Literature
[0000]
Patent Literature 1: JP 2002-249600A
Patent Literature 2: JP 2001-324616A
Patent Literature 3: JP 11-71356A
Patent Literature 4: US Patent Appn. 2007/215845
SUMMARY OF INVENTION
Technical Problem
[0012] An object of the invention is to provide a synthetic resin composition containing a triazine compound and having improved resistance to thermal coloration and an optical film and sheet obtained using the synthetic resin composition.
Solution to Problem
[0013] The inventors have conducted extensive investigations to improve thermal coloration resistance of a synthetic resin containing a triazine compound having a specific structure. As a result, they have found that a phosphite compound having a specific structure and/or a hindered phenol compound having a specific structure exhibit marked effects on the improvement of the thermal coloration resistance of a UV absorber per se comprising the triazine compound. The invention has been completed based on this finding.
[0014] The invention provides in its first aspect a UV absorber composition comprising 0.1% to 99.9% by mass of a triazine compound represented by general formula (1) (preferably a compound represented by general formula (5) shown below), 0% to 99.9% by mass of a diarylpentaerythritol diphosphite compound represented by general formula (2) and/or 0% to 99.9% by mass of an organic cyclic phosphite compound represented by general formula (3) and/or 0% to 99.9% by mass of a hindered phenol compound represented by general formula (4), provided that the total content of the compounds of formulae (2), (3), and (4) is 0.1% to 99.9% by mass:
[0000]
[0000] wherein R 1 represents a straight-chain or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 3 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylaryl group having 7 to 18 carbon atoms, or an arylalkyl group having 7 to 18 carbon atoms, the alkyl, cycloalkyl, alkenyl, aryl, alkylaryl, and arylalkyl being optionally substituted with a hydroxyl group, a halogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms and optionally interrupted by an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amido group, or an imino group, the substitution and the interruption being optionally combined with each other; R 2 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkenyl group having 3 to 8 carbon atoms; R 3 represents a hydrogen atom or a hydroxyl group; and R 4 represents a hydrogen atom or —O—R 1 ;
[0000]
[0000] wherein each of R 5 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
[0000]
[0000] wherein R 6 and R 8 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and R 7 represents an alkyl group having 1 to 18 carbon atoms;
[0000]
[0000] wherein R 9 represents a residue remaining after removing n hydroxyl groups from a mono- to tetrahydric alcohol; and n represents an integer of 1 to 4.
[0000]
[0000] wherein R 10 represents a straight-chain or branched alkyl group having 1 to 12 carbon atoms, the alkyl being optionally substituted with a hydroxyl group, a halogen atom, or an alkoxy group and optionally interrupted by an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amido group, or an imino group.
[0015] The invention provides in its second aspect a synthetic resin composition comprising 100 parts by mass of a synthetic resin (preferably an acrylic ester resin, a polycarbonate resin, a polyethylene terephthalate resin, a polyethylene naphthalate resin, a polystyrene resin, a cellulose ester resin, a cycloolefin resin, or a norbornene resin), 0.001 to 10 parts by mass of the triazine compound of the general formula (1) (preferably the compound of the general formula (5)), 0.001 to 10 parts by mass of the diarylpentaerythritol diphosphite compound of the general formula (2) and/or 0.001 to 10 parts by mass of the organic cyclic phosphite compound of the general formula (3) and/or 0.001 to 10 parts by mass of the hindered phenol compound of the general formula (4).
[0016] The invention provides in its third aspect a film or sheet (particularly an optical film or sheet, more particularly a protective film or sheet for a polarizing plate) comprising the synthetic resin composition.
Effect of the Invention
[0017] The invention allows for providing a synthetic resin composition with improved thermal coloration resistance and an optical film and sheet made from the synthetic resin composition.
DESCRIPTION OF EMBODIMENTS
[0018] The UV absorber composition, synthetic resin composition, and optical film and sheet made from the resin composition according to the invention will be described in detail based on their preferred embodiments.
[0019] The UV absorber composition of the invention will be described first.
[0020] The UV absorber composition of the invention contains 0.1% to 99.9% by mass of a triazine compound of the general formula (1), 0% to 99.9% by mass of a diarylpentaerythritol diphosphite compound of the general formula (2) and/or 0% to 99.9% by mass of an organic cyclic phosphite compound of the general formula (3) and/or 0% to 99.9% by mass of a hindered phenol compound of the general formula (4).
[0021] Examples of the C 1-C12 straight chain or branched alkyl group represented by R 1 in the general formula (1) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, undecyl, and dodecyl.
[0022] Examples of the C3-C8 cycloalkyl group represented by R 1 in the general formula (1) include cyclopropyl, cyclopentyl, cyclohexyl, and cycloheptyl.
[0023] Examples of the C6-C18 aryl group and the C7-C18 alkylaryl group represented by R 1 in the general formula (1) include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4-(2-ethylhexyl)phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-tert-butylphenyl, 2,5-di-tert-butylphenyl, 2,6-di-tert-butylphenyl, 2,4-di-tert-pentylphenyl, 2,5-di-tert-amylphenyl, 2,5-di-tert-octylphenyl, biphenyl, and 2,4,5-trimethylphenyl. Examples of the C7-C18 arylalkyl include benzyl, phenethyl, 2-phenylpropan-2-yl, and diphenylmethyl.
[0024] Examples of the C3-C8 alkenyl group represented by R 1 or R 2 in the general formula (1) include propenyl, butenyl, pentenyl, hexenyl, heptenyl, and octenyl, each of which may be straight-chain or branched and may have the unsaturated bond at any position.
[0025] Examples of the C 1-C8 alkyl group represented by R 2 in the general formula (1) include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, tert-amyl, octyl, and tert-octyl, with methyl being preferred for high UV absorption.
[0026] Examples of the triazine compound of the general formula (1) include compound Nos. 1 through 8 shown below.
[0000]
[0027] Of the triazine compounds of the general formula (1) preferred are those represented by the general formula (5) in terms of UV absorption and, from the aspect of synthetic resin physical properties, thermal coloration resistance.
[0028] The C 1-C12 alkyl group represented by R 10 in the general formula (5) is exemplified by the same groups as described for R 1 .
[0029] The triazine compound of the general formula (1) or (5) may be synthesized by any commonly used process with no particular restriction. For example, it may be synthesized by addition reaction between cyanuric chloride and a phenol derivative or a resorcinol derivative using aluminum trichloride. The substituents R 1 (R 10 ), R 2 , R 3 , and R 4 may be introduced after the formation of a triazine structure or may be introduced into the phenol compound or resorcinol derivative before the formation of a triazine structure.
[0030] The content of the triazine compound of the general formula (1) or (5) in the UV absorber composition is 0.1% to 99.9%, preferably 1% to 99%, by mass. At less than 0.1% by mass, necessary UV absorption may not be obtained. At more than 99.9% by mass, the effect on thermal coloration resistance tends to reduce.
[0031] Examples of the C1-C4 alkyl group represented by R 5 in the general formula (2) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl, with methyl being preferred in terms of ease of synthesis and effect on thermal coloration resistance.
[0032] Examples of the C1-C4 alkyl group represented by R 6 in the general formula (3) include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, and isobutyl, with tert-butyl being preferred in terms of the effects of the invention.
[0033] Examples of the C1-C18 alkyl group represented by R 7 in the general formula (3) include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, 2-heptyl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl. Examples of the substituted or interrupted alkyl include chloromethyl, dichloromethyl, trichloromethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 2,3-dihydroxypropyl, 2-hydroxy-3-methoxypropyl, 2,3-dimethoxypropyl, and 2-(2-methoxyethoxy)ethyl, with 2-ethylhexyl being preferred in terms of the effects of the invention.
[0034] In the general formula (3), R 8 is a hydrogen atom or a C1-4 alkyl group which is exemplified by the same groups given for R 6 . R 8 is preferably a hydrogen atom in view of the effects of the invention.
[0035] Examples of the organic cyclic phosphite compound of the general formula (3) include compound Nos. 9 through 11 shown below.
[0000]
[0036] In the general formula (4), R 9 is a residue remaining after removing n (n=integer of 1 to 4) hydroxyl groups from a mono- to tetrahydric alcohol. Examples of the mono- to tetrahydric alcohol include monohydric alcohols, such as methanol, ethanol, butanol, octanol, 2-ethylhexanol, decanol, dodecanol, tridecanol, isotridecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, docosanol, and triacontanol; dihydric alcohols, such as ethylene glycol, diethylene glycol, triethylene glycol, thiodiethanol, propylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 1,10-decanediol, 2,2-bis(4-(2-hydroxyethoxy)phenyl)propane, and 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane; trihydric alcohols, such as glycerol, trimethylolethane, trimethylolpropane, and tris(2-hydroxyethyl)isocyanurate; and tetrahydric alcohols, such as pentaerythritol, ditrimethylolethane, ditrimethylolpropane, and diglycerol. R 9 is preferably a residue remaining after removing four hydroxyl groups from pentaerythritol in terms of the effects of the invention.
[0037] Examples of the hindered phenol compounds of the general formula (4) are stearyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, hexamethylenebis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), thiodiethylenebis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), 2,2-bis(4-(2-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy)ethyl)phenyl)propane, tris(2-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy)ethyl)isocyanurate, and tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxymethyl)methane.
[0038] The compounds of the general formulae (2) to (4) may be synthesized through any ordinary organic synthesis with no particular restriction. The product as synthesized may be purified by an appropriate method, such as distillation, recrystallization, reprecipitation, filtration, or treatment with an adsorbent. The compounds of the general formulae (2) to (4) which are commercially available at low cost are usually supplied as a mixture, and they may be used either individually or as a mixture irrespective of the process of manufacture, composition, melting point, acid value, and so on.
[0039] The content of each of the phosphite compounds and/or hindered phenol compound of the general formulae (2) to (4) in the UV absorber composition of the invention is from 0% to 99.9%, preferably 0.1% of 99%, by mass, with the proviso that the total content of the phosphite compounds and/or hindered phenol compound of the general formulae (2) to (4) in the UV absorber composition of the invention is from 0.1% to 99.9% by mass. If the total content is less than 0.1% by mass, a sufficient effect on thermal coloration resistance is not exhibited. At a total content exceeding 99.9% by mass, the UV absorption tends to reduce.
[0040] The above illustrated UV absorber composition of the invention is incorporated into a synthetic resin hereinafter described to provide a useful synthetic resin composition.
[0041] The synthetic resin composition of the invention will then be described.
[0042] The synthetic resin composition of the invention includes 100 parts by mass of a synthetic resin, 0.001 to 10 parts by mass of the triazine compound of the general formula (1), and 0.001 to 10 parts by mass of the diarylpentaerythritol diphosphite compound of the general formula (2) and/or 0.001 to 10 parts by mass of the organic cyclic phosphite compound of the general formula (3) and/or 0.001 to 10 parts by mass of the hindered phenol compound of the general formula (4).
[0043] Examples of the synthetic resin for use in the invention include polyolefin resins, such as high density polyethylene, isotactic polypropylene, syndiotactic polypropylene, hemi-isotactic polypropylene, polybutene-1, poly(3-methyl-1-butene), poly(3-methyl-1-pentene), poly(4-methyl-1-pentene), an ethylene-propylene block or random copolymer, an ethylene-vinyl acetate copolymer, and an olefin-maleimide copolymer, and copolymers composed of monomers providing these olefin polymers; halogen-containing resins, such as polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymers, vinyl chloride-ethylene copolymers, vinyl chloride-vinylidene chloride-vinyl acetate terpolymers, vinyl chloride-acrylic ester copolymers, vinyl chloride-maleic ester copolymers, and vinyl chloride-cyclohexylmaleimide copolymers; polyester resins, such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, and polyhexamethylene terephthalate; styrene resins, such as polystyrene, high impact polystyrene (HIPS), acrylonitrile butadiene styrene copolymers (ABS), acrylonitrile chlorinated polyethylene styrene copolymers (ACS), styrene acrylonitrile copolymers (SAN), acrylonitrile butyl acrylate styrene copolymers (AAS), butadiene styrene copolymers, styrene maleic acid copolymers, styrene maleimide copolymers, acrylonitrile ethylene propylene styrene copolymers (AES), and butadiene methyl methacrylate styrene copolymers (MBS); polycarbonate resins, such as polycarbonate and branched polycarbonate; polyamide resins, including polyamides using aromatic or alicyclic dicarboxylic acids, such as polyhexamethyleneadipamide (nylon 66), polycaprolactam (nylon 6), and nylon 6T; polyphenylene oxide (PPO) resins; modified polyphenylene oxide resins; polyphenylene sulfide (PPS) resins; polyacetal (POM); modified polyacetal; polysulfone; polyether sulfone; polyether ketone; polyether imide; polyoxyethylene; petroleum resins; chroman resins; cycloolefin resins, such as norbornene resins, cycloolefin-olefin copolymer resins; polyvinyl acetate resins; polyvinyl alcohol resins; acrylic resins, such as polymethyl methacrylate; polycarbonate/styrene resin polymer alloys; polyvinyl alcohol resins; cellulose resins, such as diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetylpropionyl cellulose, and nitrocellulose; liquid crystal polymers (LCP); silicone resins; urethane resins; biodegradable resins, such as aliphatic polyesters obtained from aliphatic dicarboxylic acids, aliphatic diols, aliphatic hydroxycarboxylic acids, or cyclic derivatives thereof and the aliphatic polyesters having molecular weights increased by using a diisocyanate compound; and recycled resins thereof. Further included are thermosetting resins, such as phenol resins, urea resins, melamine resins, epoxy resins, and unsaturated polyester resins. Rubbery polymers are also useful, such as natural rubber (NR), polyisoprene rubber (IR), styrene butadiene rubber (SBR), polybutadiene rubber (BR), ethylene-propylene-diene rubber (EPDM), butyl rubber (IIR), chloroprene rubber, acrylonitrile butadiene rubber (NBR), and silicone rubber. For applications to optical materials, polycarbonate resins, polyethylene terephthalate resins, polyethylene naphthalate resins, cellulose ester resins, such as cellulose triacetate and cellulose acetate butyrate, acrylic ester resins, such as polymethyl acrylate and polymethyl methacrylate, cycloolefin resins, polystyrene resins, and norbornene resins, all of which are excellent in visible light transmittance, are preferred for their excellence in transparency, durability, polarization characteristics, and electrical insulating properties.
[0044] The description of the triazine compound of the general formula (1) or (5), the diarylpentaerythritol diphosphite compound of the general formula (2), the organic cyclic phosphite compound of the general formula (3), and the hindered phenol compound of the general formula (4) given with respect to the UV absorber composition appropriately applies to the corresponding compounds for use in the synthetic resin composition.
[0045] The amount of the triazine compound of the general formula (1) or (5) to be added to a synthetic resin is 0.001 to 10 parts, preferably 0.01 to 5 parts, by mass per 100 parts by mass of the synthetic resin. At less than 0.001 parts by mass, a sufficient stabilization effect is not obtained. At more than 10 parts by mass, problems, such as a reduction in physical properties of the resin and impairment of the appearance of the resin composition due to blooming, occur.
[0046] The amount of each of the phosphite compounds and hindered phenol compound of the general formulae (2) to (4) to be added to a synthetic resin is 0.001 to 10 parts, preferably 0.01 to 5 parts, by mass per 100 parts by mass of the synthetic resin. The total amount of the phosphite compounds and hindered phenol compound of the general formulae (2) to (4) should be within the range of from 0.001 to 10 parts by mass per 100 parts by mass of the synthetic resin. When the total amount is less than 0.001 parts by mass, a sufficient inhibitory effect on thermal coloration is not exhibited. If it exceeds 10 parts by mass, problems, such as a reduction in physical properties of the synthetic resin and impairment of the appearance of the synthetic resin due to bleeding, occur.
[0047] The synthetic resin composition of the invention may contain commonly used additives in accordance with the resin, such as other antioxidants (e.g., phenol antioxidants, phosphorous antioxidants, or thioether antioxidants), other UV absorbers (e.g., benzotriazole UV absorbers, other triazine UV absorbers, and benzophenone UV absorbers), hindered amine light stabilizers, plasticizers, and processing aids.
[0048] Examples of the phenol antioxidant include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, 4,4′-thiobis(6-tert-butyl-m-cresol), 2,2′-methylidenebis(4-methyl-6-tert-butylphenol), 2,2′-methylenebis(4-ethyl-6-tert-butylphenol), 4,4′-butylidenebis(6-tert-butyl-m-cresol), 2,2′-ethylidenebis(4,6-di-tert-butylphenol), 2,2′-ethylidenebis(4-sec-butyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl)phenol, thiodiethylene glycol bis[(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid] glycol ester, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl] terephthalate, 1,3,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl] isocyanurate, 3,9-bis[1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl) prionyloxy}ethyl]-2,4, 8,10-tetraoxaspiro[5.5]undecane, and triethylene glycol bis[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate. The phenol antioxidant is used in an amount preferably of 0.001 to 10 parts, more preferably 0.05 to 5 parts, by mass per 100 parts by mass of the synthetic resin.
[0049] Examples of the phosphorus antioxidant include trisnonylphenyl phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl] phosphite, tridecyl phosphite, octyldiphenyl phosphite, di(decyl)monophenyl phosphite, di(tridecyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, tetra(tridecyl)isopropylidenediphenol diphosphite, tetra(tridecyl)-4,4′-n-butylidenebis(2-tert-butyl-5-methylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide, 2,2′-ethylidenebis(4,6-di-tert-butylphenyl)fluorophosphite, tris(2-[(2,4,8,10-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl)amine, and 2-ethyl-2-butyl propylene glycol 2,4,6-tri-tert-butylphenol phosphite.
[0050] Examples of the thioether antioxidant include dialkyl thiodipropionates, such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and β-alkylmercaptopropionic acid polyol esters, such as pentaerythritol tetra(β-dodecylmercaptopropionate).
[0051] Examples of the benzotriazole UV absorbers include 2-(2′-hydroxyphenyl)benzotriazoles, such as 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(2′-hydroxy-3′,5′-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2′-hydroxy-3′-tert-butyl-5′-methylphenyl)-5-chlorobenzotriazole, 2-(2′-hydroxy-5′-tert-octylphenyl)benzotriazole, 2-(2′-hydroxy-3′,5′-dicumylphenyl)benzotriazole, 2-(2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl)benzotriazole, and 2,2′-methylenebis(4-tert-octyl-6-benzotriazolyl)phenol.
[0052] Examples of the triazine UV absorbers include triaryltriazines, such as 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2,4-dimethylphenyl)-s-triazine, 2-(2-hydroxy-4-hexyloxyphenyl)-4,6-diphenyl-s-triazine, 2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-dimethylphenyl)-s-triazine, 2-(2-hydroxy-4-hexyloxyphenyl)-4,6-dibiphenyl-s-triazine, 2,4-bis(2-hydroxy-4-octoxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine, and 2,4,6-tris(2-hydroxy-4-octoxyphenyl)-s-triazine.
[0053] Examples of the benzophenone UV absorbers include 2-hydroxybenzophenones, such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis(2-hydroxy-4-methoxybenzophenone).
[0054] Examples of the hindered amine light stabilizers include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-piperidyl methacrylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl) bis(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) bis(tridecyl) 1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) 2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, 3,9-bis[1,1-dimethyl-2-[tris(2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy)butylcarbonyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 3,9-bis[1,1-dimethyl-2-[tris(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyloxy)butylcarbonyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,6-bis(2,2,6,6-tetramethyl-4-piperidyl amino)hexane/2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8,12-tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-ylamino]undecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-ylamino]undecane, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol/diethyl succinate polycondensate, and 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/dibromoethane polycondensate.
[0055] It is preferred for the other antioxidants, UV absorbers, and hindered amine light stabilizers to have a structure providing high solubility in the base resin and to have a high molecular weight, specifically 500 or more, more preferably 700 or more, to be sparingly volatile with heat applied in processing or on use. The other antioxidants and UV absorbers may have a polymerizable group or a reactive group introduced therein to gain in molecular weight or to be incorporated into a resin molecule. The amount of the other antioxidants and UV absorbers to be used is preferably 0.01 to 10 parts, more preferably 0.05 to 5 parts, by mass per 100 parts by mass of the synthetic resin.
[0056] Useful plasticizers include, but are not limited to, phosphoric ester plasticizers and polyester plasticizers. These plasticizers may be used either alone or in combination of two or more thereof.
[0057] Examples of the phosphoric ester plasticizers include triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, octyldiphenyl phosphate, diphenylbiphenyl phosphate, trioctyl phosphate, and tributyl phosphate.
[0058] Examples of the polyester plasticizers are acyclic polyesters composed of an aliphatic or aromatic dibasic acid and a diol compound and acyclic polyesters of hydroxycarboxylic acids.
[0059] Examples of the aliphatic dibasic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, fumaric acid, 2,2-dimethylglutaric acid, suberic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, diglycolic acid, itaconic acid, maleic acid, and 2,5-norbornenedicarboxylic acid. Examples of the aromatic dibasic acid include phthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, anthracenedicarboxylic acid, and terphenyldicarboxylic acid.
[0060] Examples of the diol compound include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-methylpropanediol, 1,3-dimethylpropanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2,2,4-trimethyl-1,6-hexanediol, 2-ethyl-2-butylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, thiodiethylene glycol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5,5] undecane.
[0061] Examples of the hydroxycarboxylic acid are 4-hydroxymethylcyclohexanecarboxylic acid, hydroxytrimethylacetic acid, 6-hydroxycapronic acid, glycolic acid, and lactic acid.
[0062] Other polyester plasticizers include those formed between tri- or higher functional polyols and monocarboxylic acid compounds. Examples of the tri- or higher functional polyols include glycerol, trimethylolpropane, pentaerythritol, sorbitol, and condensates thereof, e.g., dipentaerythritol and tripentaerythritol. Polyether polyols obtained by adding an alkylene oxide (e.g., ethylene oxide) to these polyols are also useful.
[0063] Examples of the monocarboxylic acid include aromatic carboxylic acids, such as benzoic acid, p-methylbenzoic acid, m-methylbenzoic acid, dimethylbenzoic acid, p-tert-butylbenzoic acid, p-methoxybenzoic acid, p-chlorobenzoic acid, naphthylic acid, and biphenylcarboxylic acid; alicyclic carboxylic acids, such as cyclohexanecarboxylic acid; and aliphatic carboxylic acids, such as acetic acid, propionic acid, and 2-ethylhexanoic acid. These monocarboxylic acids may be used either individually or as a mixture thereof.
[0064] The amount of the plasticizer to be used preferably ranges from 0 to 20% by mass relative to the synthetic resin in terms of synthetic resin properties and processing properties. For use in an element of LCDs, the amount is more preferably 1% to 15% by mass, even more preferably 2% to 10% by mass in terms of dimensional stability. The polyester plasticizers are particularly preferred from the standpoint of hydrolysis.
[0065] In the preparation of the synthetic resin composition of the invention, the order of mixing the synthetic resin, the triazine compound, phosphite compound, and hindered phenol compound of the general formulae (1) to (5), and the above discussed additives is not particularly limited. All the components may be mixed up at once, the synthetic resin may be mixed with a separately prepared UV absorber composition, a separately prepared mixture of a plurality of components may be mixed with the others, or separately prepared mixtures of a plurality of components may be mixed together.
[0066] When a separately prepared UV absorber composition is compounded into a synthetic resin to provide the synthetic resin composition of the invention, the UV absorber composition is used preferably in an amount of 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the synthetic resin.
[0067] The above described synthetic resin composition of the invention is expected to be advantageous in that it exhibits good adhesion to a substrate (e.g., a polarizing plate), provides a resin film with stable physical properties, and does not stain an adjacent element because the triazine compound, phosphite compound, and hindered phenol compound of the general formulae (1) to (5) have high solubility in the synthetic resins recited above, particularly those suited for use as an optical material, such as acrylic ester resins, polycarbonate resins, polyethylene terephthalate resins, polyethylene naphthalate resins, polystyrene resins, cellulose ester resins, and norbornene resins.
[0068] While the application of the synthetic resin composition of the invention is not particularly limited, the synthetic resin composition is suitably formed into sheet or film for use as an optical material, such as an optical film or sheet. It is also useful as a material of coatings. The optical material is exemplified by optical films or sheets in image display apparatus, such as liquid crystal displays (LCDs), plasma display panels (PDPs), electroluminescence displays (ELDs), cathode ray tube displays (CRTs), fluorescent display tubes, and field emission displays. The synthetic resin composition is especially useful as optical films in LCDs or organic ELDs which contain in their display elements organic materials having poor UV resistance. The optical films used in organic ELDs include an optical correction film and a protective film for a light emitting element. The optical films or sheets used in LCDs include a protective film or sheet for a polarizing plate, a retardation film, a retardation film, a viewing angle compensation film, an antiglare film, a luminance-improving film, a diffuser film or sheet, a lens film or sheet, an antifog film, an antistatic film, an optical correction film, an antireflection film, a color adjusting film, and a light guide film. In particular, the synthetic resin composition is suitable for use as an optical film or sheet disposed on the outer side of a polarizing plate provided in contact with a liquid crystal cell or a protective film or sheet for a polarizing plate.
[0069] Application of the synthetic resin composition of the invention as an optical film or sheet will be described.
[0070] The optical film or sheet according to the invention is obtained by molding the synthetic resin composition of the invention into film or sheet. The molding may be performed in a conventional manner, such as solvent casting, injection molding, or melt extrusion. The film or sheet thickness is not particularly limited. The thickness of a molded film is preferably 5 to 300 μm, more preferably 5 to 150 μm, and that of a molded sheet is preferably 200 μm to 10 mm, more preferably 300 μm to 5 mm.
[0071] Since the triazine compound, phosphite compounds, and hindered phenol compound of the general formulae (1) to (4) contained in the synthetic resin composition have good resistance against volatilization, the optical film or sheet of the invention may advantageously be obtained by solvent casting, injection molding, or melt extrusion using the synthetic resin composition under high temperature conditions (e.g., 200° to 350° C.), which are highly productive.
[0072] An LCD having the optical film or sheet of the invention is superior in retention of polarizing ability. The optical film or sheet is suitably applicable to any type of LCDs irrespective of the driving mode (e.g., TN, STN, or TFT), the light source (e.g., a backlight, a fluorescent lamp, or an LED), whether or not external light such as sunlight is used (i.e., whether reflective or transmissive), whether with or without an added display function (such as a touch panel function), or whether with or without, or a degree of, a measure for functional improvement.
EXAMPLES
[0073] The invention will now be illustrated in greater detail with reference to Examples, but it should be understood that the invention is not deemed to be limited thereto. Unless otherwise noted, all the parts are by mass.
Example 1 and Comparative Example 1
[0074] A mixture of 1 part of the triazine compound shown in Table 1 or 2 below and 0.02 parts of the phosphite compound or the hindered phenol compound shown in Table 1 or 2 was put in a test tube, heated in a dry block bath at 300° C. for 15 minutes, and cooled at room temperature for 1 hour. The degree of coloration after cooling was observed with the naked eye and rated according to the following rating system. The results obtained are shown in Tables 1 and 2.
[0000] Rating system for evaluating coloration by visual observation (1 to 5 scale)
1: Faintly colored (pale yellow)
2: Lightly colored (yellowish brown)
3: Medium colored (reddish brown)
4: Deeply colored (blackish brown)
5: Blackened
[0075]
[0000]
TABLE 1
Example
1-1
1-2
1-3
Compound of General Formula (1)
No. 4
No. 4
No. 7
Compound of General Formula (2), (3) or (4)
No. 10
No. 12
No. 12
Comparative Compound
—
—
—
Coloration (visual observation)
1
1
2
[Chem. 17]
[0000]
TABLE 2
Comparative Example
1-1
1-2
1-3
1-4
1-5
1-6
1-7
Compound of General Formula (1)
No. 4
No. 4
No. 4
No. 4
No. 4
No. 4
No. 4
Compound of General Formula (2), (3) or (4)
—
—
—
—
—
—
—
Comparative Compound
No. 13
No. 14
No. 15
No. 16
No. 17
No. 18
—
Coloration (visual observation)
5
5
5
5
5
5
5
[Chem. 18]
[Chem. 19]
[Chem. 20]
[Chem. 21]
[Chem. 22]
[Chem. 23]
Example 2 and Comparative Example 2
Making of Pellets
[0076] A hundred parts of the synthetic resin shown in Table 3 or 4 below, 1 part of the compound No. 4, and the compound(s) shown in tables were compounded, and the resulting mixture was extruded using an extruder Laboplastomill Micro (from Toyo Seiki Kogyo) into pellets at the processing temperature shown in the tables.
[0077] The synthetic resins used were as follows.
[0000] PC: Polycarbonate resin: E-2000, from Mitsubishi Engineering Plastics
NBE: Norbornene resin: ARTON F5023, from JSR
PET: Polyethylene terephthalate resin: TR-8550, from Teijin Chemicals
PS: Polystyrene resin: reagent code: 182427, from Aldrich
PMMA: Methacrylic resin: Acrypet VH000, from Mitsubishi Rayon
CAB: Cellulose acetate butyrate resin: CAB 381-20, from Eastman Chemical
Method of Evaluating Thermal Coloration Resistance
[0078] To evaluate thermal coloration resistance, the yellow index (Y.I.) in reflection of the pellets was measured using a spectrophotometric colorimeter with multiple light sources from Suga Test Instruments. The results obtained are shown in Tables 3 and 4.
[0000]
TABLE 3
Example
Comparative Example
2-1-1
2-1-2
2-1-3
2-2-1
2-3-1
2-3-2
2-3-3
2-1
2-2
2-3
Synthetic Resin
PC
PET
NBE
PC
PET
NBE
Processing Temp. (° C.)
260
280
260
260
280
260
Compound No. 12
0.05
—
0.05
0.05
0.05
—
0.05
—
—
—
Compound No. 19
—
0.05
0.05
0.05
—
0.05
0.05
—
—
—
Y.I. (reflection)
41.4
44.2
39.5
33.0
34.8
35.3
34.1
46.7
37.0
37.1
[0000]
TABLE 4
Example
Comparative Example
2-4-1
2-4-2
2-5-1
2-5-2
2-6-1
2-6-2
2-4
2-5
2-6
Synthetic Resin
PS
PMMA
CAB
PS
PMMA
CAB
Processing Temp. (° C.)
230
260
220
230
260
220
Compound No. 12
0.05
0.05
—
0.05
0.05
0.05
—
—
—
Compound No. 19
—
0.05
0.05
0.05
—
0.05
—
—
—
Y.I. (reflection)
41.0
40.5
37.1
37.0
58.1
56.4
43.5
40.1
62.0
[Chem. 24]
[0079] It is seen from the results in Tables 1 through 4 that the triazine compound having a specific structure according to the invention brings about a remarkable improvement on thermal coloration resistance (ΔY.I.) in various synthetic resins only when combined with the phosphite compound(s) and/or hindered amine compound having specific structures according to the invention.
[0080] The specific phosphite compounds and/or hindered phenol compound according to the invention are considerably effective in improving thermal coloration resistance of the triazine compound-containing synthetic resin of the invention and provide a UV absorbent composition and a synthetic resin composition containing the UV absorbent composition, both of which exhibit excellent resistance to thermal discoloration. In particular, they are very useful in improving the thermal coloration resistance of synthetic resins used in optical films and sheet. | A synthetic resin composition is obtained by mixing, to 100 parts by mass of a synthetic resin, 0.001-10 parts by mass of a triazine-based compound represented by general formula (1), 0.001-10 parts by mass of a diaryl pentaerythritol diphosphite compound represented by general formula (2), and/or 0.001-10 parts by mass of an organic cyclic phosphite compound represented by general formula (3), and/or 0.001-10 parts by mass of a hindered phenolic compound represented by general formula (4). (In formula (1), R1 represents an alkyl group having 1-12 carbon atoms, R2 represents an alkyl group having 1-8 carbon atoms, R3 represents a hydroxy group, and R4 represents —O—R1. In formula (2), R5 represents an alkyl group having 1-4 carbon atoms. In formula (3), R5 and R8 represent an alkyl group having 1-4 carbon atoms, and R7 represents an alkyl group having 1-18 carbon atoms. In formula (4), R9 represents a residue obtained by removing n hydroxyl groups from a monovalent to tetravalent alcohol, and n represents an integer 1-4.) | 8 |
BACKGROUND OF THE INVENTION
The present invention relates to an improved carding apparatus in which the standard of the sliver produced is good enough to allow the sliver to be fed directly to a spinning operation or to a combing operation without the need for further doubling and drafting.
PRIOR ART
It is known to provide carding apparatus having an autoleveller which reduces the irregularities in density or thickness of the product sliver. Autolevellers can operate to reduce either long term fluctuation which may involve wavelengths which extend over many metres of length of the finished sliver due to variations in the input material, or may compensate for much shorter term fluctuations involving fractions of a metre in wave length. The present invention is particularly applicable to a short term autoleveller on carding apparatus, although it is conceivable to combine both short term and long term autolevelling if desired.
An autoleveller relies on varying the draft of a sliver just downstream of a sliver density or thickness measuring sensor so that the variations sensed by that sensor can be eliminated by increasing the draft temporarily to reduce sliver thickness or density or by reducing the draft ratio temporarily to increase the density or thickness.
OBJECT OF THE INVENTION
It is an object of the present invention to improve still further on the quality of the sliver produced from a short term autoleveller incorporated in or downstream of carding apparatus.
SUMMARY OF THE INVENTION
Accordingly, one aspect of the present invention provides a process of carding a fibrous web to form a sliver, comprising carding the web, and then immediately condensing the carded web to form a sliver and subjecting the thus formed sliver to an initial drafting operation and then autolevelling the thus drafted sliver downstream of the point of completion of the initial drafting operation.
A second aspect of the present invention provides carding apparatus comprising means for condensing the carded web to form a sliver, a drafting set operative to draft the thus condensed sliver, and downstream of the drafting set an autoleveller including variable draft means for autolevelling the drafted sliver.
BRIEF DESCRIPTION OF THE DRAWING
In order that the present invention may more readily be understood the following description is given, merely by way of example, with reference to the accompanying drawing in which the sole FIGURE shows one embodiment of 9- drafting/carding apparatus in accordance with the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the drawing, there is shown a carding cylinder 1 to which a fibrous web or batt is introduced by a taker-in 2, and from which the carded web is removed by means of a doffer 3. The web is then in turn removed from the doffer 3 by a web take-off roll 4. The carding of fibres being carried by the carding cylinder 1 is effected by way of card clothing on a concave part-cylindrical carding plate 5 which is thus held close to the path of movement of card clothing on the cylinder 1, so that the web being carried by the cylinder 1 is carded between the opposed points of (i) the card clothing of the cylinder 1 and (ii) that on the plate 5, respectively.
In a known manner, the web removed by the take-off roll 4 is then applied to a conveyor belt web condensing system 6 which draws the edges of the web inwardly towards the centre of the web in order to condense the web to form a sliver.
Other forms of web condensing apparatus are known and are suitable for the present invention, such apparatus including a lateral draw belt take-off arrangement in which the sliver is condensed along one edge of the web rather than along the centre of the web, or a condensing trumpet arrangement in which the edges of the web are progressively brought inwardly to the centre to be condensed to form a sliver. However, the centre draw conveyor belt arrangement mentioned above is preferred.
In EP-A-0354653 the sliver from the belt take-up condensing system is passed between tongue-and-groove rollers of the autoleveller, to a "two over three" roller drafting system. However, in the present apparatus the sliver is first of all passed through a "three over three" drafting set 7 from which it then passes between a tongue-and-groove roller pair 8 comprising an upper tongue roller 9 whose periphery engages in a groove of a lower groove roller 10.
From the tongue-and-groove roller pair 8 the sliver then passes through a "two over three" drafting roller set 11 comprising a first nip defined by upper roller 12 engaging lower rollers 13 and 14 to clamp the sliver thereagainst, and a second drafting nip comprising an upper drafting roll 15 and a lower drafting roll 16.
From the final drafting pair 15, 16 the sliver is then fed by way of a coiler into a sliver can for storage purposes. However, as indicated above, the material could if desired be fed straight to a comber or to a spinning stage such as an open-end spinning machine without needing to be stored in a can.
In the preferred embodiment of the present invention where the sliver is stored before further processing, the coiler includes a further tongue-and-groove roller pair comprising a groove roller 17 whose groove is engaged by the periphery of a tongue roller 18, for the purposes of monitoring the uniformity of the sliver passing into the can at the coiler.
Both the tongue-and-groove roller pair 8 and the tongue-and-groove rollers 17 and 18 of the coiler are, as is conventional, arranged so that one, for example the tongue roller 9 or 18, can be yieldably displaced towards and away from the other (the groove roller 10 or 17) with means for sensing the changes in spacing between the axes of the tongue-and-groove rollers of the respective pairs in order to detect variations in thickness of the sliver passing between the tongue-and-groove rollers. The displacement sensor provides a signal to indicate sliver thickness, and in the case of the tongue-and-groove roller pair 8 this signal is used to vary the draft in the drafting set 11, but in the case of the tongue-and-groove rollers 18 and 17 the displacement signal is intended to provide a monitor of sliver uniformity, for the purposes of rejecting any sliver whose quality is out of limits when passing through the coiler. In practice, however, the reliability of the uniformity imparted by the apparatus shown in the drawing is such that this sliver thickness monitoring at the rollers 17 and 18 is simply a guarantee of uniformity and not a positive rejection mechanism.
In the first "three over three" drafting roller set 7, the first pair of drafting rollers 19 and 20 are fixed in position, whereas means 30 are provided for moving the second pair of drafting rollers 21 and 22 as a pair towards and away from the first pair 19, 20, in order to adjust the length of the "breaking draft" zone between them to accommodate different lengths of fibre staple length. Similarly, means 31 are provided for moving the third pair of drafting rollers 23, 24 adjustable for positioning towards and away from the second pair 21, 22 for varying the length of the "actual draft" zone between rollers 21, 22 on the one hand and rollers 23, 24 on the other hand.
We prefer the draft imposed at the autolevelling stage in the "two over three" drafting roller set 11 to be of the order of 1.5 in the steady state, but varied by increasing and decreasing the draft in order to restore sliver thickness uniformity. A more preferable draft at the drafting set 11 may be of the order of 1.3:1 in order to improve the autolevelling efficiency. The draft required at the autolevelling stage is simply enough to ensure that there is adequate scope for draft reduction to eliminate variations of the maximum amplitude likely to be encountered. It is not intended that there should be any strong drafting action at the drafting set 11.
At the drafting set 7, the overall draft may be as high as 30, although the draft value may be chosen depending on the next stage of treatment of the sliver leaving the autoleveller final drafting nip 15, 16. Higher drafts, for example of the order of 16:1, may be preferred where the sliver is to be subjected to a downstream combing operation, but if direct feed of the sliver to an open-end spinner is sought after then an overall draft of the order of 12:1 at the drafting set 7 is preferred.
For optimum overall quality of the sliver a draft of from 6:1 to 8:1 is preferred. | A sliver is created by directly condensing the carded web from a carding apparatus and then feeding it to a drafting set from which it is subsequently delivered by way of an autoleveller comprising sliver thickness sensing means and variable draft means. | 3 |
RELATED APPLICATIONS
This application is a national phase application under 35 U.S.C. §371 of PCT International Application No. PCT/US2007/062152, filed on Feb. 14, 2007, which claims priority under 35 U.S.C. §119(e) to U.S. provisional patent application, U.S. Ser. No. 60/773,172, filed Feb. 14, 2006. Each of these prior applications is incorporated herein by reference.
BACKGROUND OF THE INVENTION
The identification of small organic molecules that affect specific biological functions is an endeavor that impacts both biology and medicine. Such molecules are useful as therapeutic agents and as probes of biological function. In but one example from the emerging field of chemical genetics, in which small molecules can be used to alter the function of biological molecules to which they bind, these molecules have been useful at elucidating signal transduction pathways by acting as chemical protein knockouts, thereby causing a loss of protein function (Schreiber et al., J. Am. Chem. Soc., 1990, 112, 5583; Mitchison, Chem. and Biol., 1994, 1, 3). Additionally, due to the interaction of these small molecules with particular biological targets and their ability to affect specific biological function, they may also serve as candidates for the development of therapeutics. One important class of small molecules, natural products, which are small molecules obtained from nature, clearly have played an important role in the development of biology and medicine, serving as pharmaceutical leads, drugs (Newman et al., Nat. Prod. Rep. 2000, 17, 215-234), and powerful reagents for studying cell biology (Schreiber, S. L. Chem. and Eng. News 1992 (October 26), 22-32).
Because it is difficult to predict which small molecules will interact with a biological target, and it is often difficult to obtain and synthesize efficiently small molecules found in nature, intense efforts have been directed towards the generation of large numbers, or libraries, of small organic compounds, often “natural product-like” libraries. These libraries can then be linked to sensitive screens for a particular biological target of interest to identify the active molecules.
One biological target of recent interest is histone deacetylase (see, for example, a discussion of the use of inhibitors of histone deacetylases for the treatment of cancer: Marks et al Nature Reviews Cancer 2001, 1, 194; Johnstone et al. Nature Reviews Drug Discovery 2002, 1, 287). Post-translational modification of proteins through acetylation and deacetylation of lysine residues has a critical role in regulating their cellular functions. HDACs are zinc hydrolases that modulate gene expression through deacetylation of the N-acetyl-lysine residues of histone proteins and other transcriptional regulators (Hassig et al. Curr. Opin. Chem. Biol. 1997, 1, 300-308). HDACs participate in cellular pathways that control cell shape and differentiation, and an HDAC inhibitor has been shown effective in treating an otherwise recalcitrant cancer (Warrell et al. J. Natl. Cancer Inst. 1998, 90, 1621-1625). Eleven human HDACs, which use Zn as a cofactor, have been characterized (Taunton et al. Science 1996, 272, 408-411; Yang et al. J. Biol. Chem. 1997, 272, 28001-28007; Grozinger et al. Proc. Natl. Acad. Sci. U.S.A. 1999, 96, 4868-4873; Kao et al. Genes Dev. 2000, 14, 55-66; Hu et al J. Biol. Chem. 2000, 275, 15254-15264; Zhou et al. Proc. Natl. Acad. Sci. U.S.A. 2001, 98, 10572-10577; Venter et al. Science 2001, 291, 1304-1351). These members fall into three related classes (class I, II, and III). An additional seven HDACs have been identified which use NAD as a confactor. To date, no small molecules are known that selectively target either the two classes or individual members of this family ((for example ortholog-selective HDAC inhibitors have been reported: (a) Meinke et al. J. Med. Chem. 2000, 14, 4919-4922; (b) Meinke, et al. Curr. Med. Chem. 2001, 8, 211-235).
SUMMARY OF THE INVENTION
The present invention provides novel histone deacetylase inhibitors and methods of preparing and using these compounds. The inventive HDAC inhibitors comprise an esterase-sensitive ester linkage, thereby when the compound is exposed to an esterase such as in the bloodstream the compound is inactivated. The compounds are particularly useful in the treatment of skin disorders such as cutaneous T-cell lymphoma, neurofibromatosis, psoriasis, hair loss, dermatitis, baldness, and skin pigmentation. The inventive compound is administered topically to the skin of the patient where it is clinically active. Once the compound is absorbed into the body, it is quickly inactivated by esterases which cleave the compound into two or more biologically inactive fragments. Thus, allowing for high local concentrations (e.g., in the skin) and reduced systemic toxicity. In certain embodiments, the compound is fully cleaved upon exposure to serum in less than 5 min., preferably less than 1 min.
The present invention provides novel compounds of general formula (I),
and pharmaceutical compositions thereof, as described generally and in subclasses herein, which compounds are useful as inhibitors of histone deacetylases or other deacetylases, and thus are useful for the treatment of proliferative diseases. The inventive compounds are additionally useful as tools to probe biological function. In certain embodiments, the compounds of the invention are particularly useful in the treatment of skin disorders. The ester linkage is susceptible to esterase cleavage, particularly esterases found in the blood. Therefore, these compounds may be administered topically to treat skin disorders, such as cutaneous T-cell lymphoma, psoriasis, hair loss, dermatitis, etc., without the risk of systemic effects. Once the compound enters the bloodstream it is quickly degraded by serum esterases. Preferably, the compound is degraded into non-toxic, biologically inactive by-products.
In another aspect, the present invention provides methods for inhibiting histone deacetylase activity or other deacetylase activity in a patient or a biological sample, comprising administering to said patient, or contacting said biological sample with an effective inhibitory amount of a compound of the invention. In certain embodiments, the compounds specifically inhibit a particular HDAC (e.g., HDAC1, HDAC2, HDAC3, HDAC4, HDAC4, HDAC5, HDAC6, HDAC7, HDAC8, HDAC9, HDAC10, HDAC11) or class of HDACs (e.g., Class I, II, or III). In certain embodiments, the compounds specifically inhibit HDAC6. In still another aspect, the present invention provides methods for treating skin disorders involving histone deacetylase activity, comprising administering to a subject in need thereof a therapeutically effective amount of a compound of the invention. The compounds may be administered by any method known in the art. In certain embodiments, the compounds are administered topically (e.g., in a cream, lotion, ointment, spray, gel, powder, etc.). In certain embodiments, the compound is administered to skin. In other certain embodiments, the compound is administered to hair. The compounds may also be administered intravenously or orally. The invention also provides pharmaceutical compositions of the compounds wherein the compound is combined with a pharmaceutically acceptable excipient.
In yet another aspect, the present invention provides methods for preparing compounds of the invention and intermediates thereof.
Definitions
Certain compounds of the present invention, and definitions of specific functional groups are also described in more detail below. For purposes of this invention, the chemical elements are identified in accordance with the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75 th Ed., inside cover, and specific functional groups are generally defined as described therein. Additionally, general principles of organic chemistry, as well as specific functional moieties and reactivity, are described in Organic Chemistry, Thomas Sorrell, University Science Books, Sausalito: 1999, the entire contents of which are incorporated herein by reference. Furthermore, it will be appreciated by one of ordinary skill in the art that the synthetic methods, as described herein, utilize a variety of protecting groups. By the term “protecting group,” has used herein, it is meant that a particular functional moiety, e.g., C, O, S, or N, is temporarily blocked so that a reaction can be carried out selectively at another reactive site in a multifunctional compound. In preferred embodiments, a protecting group reacts selectively in good yield to give a protected substrate that is stable to the projected reactions; the protecting group must be selectively removed in good yield by readily available, preferably nontoxic reagents that do not attack the other functional groups; the protecting group forms an easily separable derivative (more preferably without the generation of new stereogenic centers); and the protecting group has a minimum of additional functionality to avoid further sites of reaction. As detailed herein, oxygen, sulfur, nitrogen and carbon protecting groups may be utilized. Exemplary protecting groups are detailed herein, however, it will be appreciated that the present invention is not intended to be limited to these protecting groups; rather, a variety of additional equivalent protecting groups can be readily identified using the above criteria and utilized in the method of the present invention. Additionally, a variety of protecting groups are described in Protective Groups in Organic Synthesis, Third Ed. Greene, T. W. and Wuts, P. G., Eds., John Wiley & Sons, New York: 1999, the entire contents of which are hereby incorporated by reference. Furthermore, a variety of carbon protecting groups are described in Myers, A.; Kung, D. W.; Zhong, B.; Movassaghi, M.; Kwon, S. J. Am. Chem. Soc. 1999, 121, 8401-8402, the entire contents of which are hereby incorporated by reference.
It will be appreciated that the compounds, as described herein, may be substituted with any number of substituents or functional moieties. In general, the term “substituted” whether preceded by the term “optionally” or not, and substituents contained in formulas of this invention, refer to the replacement of hydrogen radicals in a given structure with the radical of a specified substituent. When more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituent may be either the same or different at every position. As used herein, the term “substituted” is contemplated to include all permissible substituents of organic compounds. In a broad aspect, the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds. For purposes of this invention, heteroatoms such as nitrogen may have hydrogen substituents and/or any permissible substituents of organic compounds described herein which satisfy the valencies of the heteroatoms. Furthermore, this invention is not intended to be limited in any manner by the permissible substituents of organic compounds. Combinations of substituents and variables envisioned by this invention are preferably those that result in the formation of stable compounds useful in the treatment, for example of proliferative disorders, including, but not limited to cancer. The term “stable”, as used herein, preferably refers to compounds which possess stability sufficient to allow manufacture and which maintain the integrity of the compound for a sufficient period of time to be detected and preferably for a sufficient period of time to be useful for the purposes detailed herein.
The term “acyl”, as used herein, refers to a carbonyl-containing functionality, e.g., —C(═O)R″ wherein R′ is an aliphatic, alycyclic, heteroaliphatic, heterocyclic, aryl, heteroaryl, (aliphatic)aryl, (heteroaliphatic)aryl, heteroaliphatic(aryl) or heteroaliphatic(heteroaryl) moiety, whereby each of the aliphatic, heteroaliphatic, aryl, or heteroaryl moieties is substituted or unsubstituted, or is a substituted (e.g., hydrogen or aliphatic, heteroaliphatic, aryl, or heteroaryl moieties) oxygen or nitrogen containing functionality (e.g., forming a carboxylic acid, ester, or amide functionality).
The term “aliphatic”, as used herein, includes both saturated and unsaturated, straight chain (i.e., unbranched) or branched aliphatic hydrocarbons, which are optionally substituted with one or more functional groups. As will be appreciated by one of ordinary skill in the art, “aliphatic” is intended herein to include, but is not limited to, alkyl, alkenyl, alkynyl moieties. Thus, as used herein, the term “alkyl” includes straight and branched alkyl groups. An analogous convention applies to other generic terms such as “alkenyl”, “alkynyl” and the like. Furthermore, as used herein, the terms “alkyl”, “alkenyl”, “alkynyl” and the like encompass both substituted and unsubstituted groups. In certain embodiments, as used herein, “lower alkyl” is used to indicate those alkyl groups (substituted, unsubstituted, branched or unbranched) having 1-6 carbon atoms.
In certain embodiments, the alkyl, alkenyl and alkynyl groups employed in the invention contain 1-20 aliphatic carbon atoms. In certain other embodiments, the alkyl, alkenyl, and alkynyl groups employed in the invention contain 1-10 aliphatic carbon atoms. In yet other embodiments, the alkyl, alkenyl, and alkynyl groups employed in the invention contain 1-8 aliphatic carbon atoms. In still other embodiments, the alkyl, alkenyl, and alkynyl groups employed in the invention contain 1-6 aliphatic carbon atoms. In yet other embodiments, the alkyl, alkenyl, and alkynyl groups employed in the invention contain 1-4 carbon atoms. Illustrative aliphatic groups thus include, but are not limited to, for example, methyl, ethyl, n-propyl, isopropyl, allyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, tert-pentyl, n-hexyl, sec-hexyl, moieties and the like, which again, may bear one or more substituents. Alkenyl groups include, but are not limited to, for example, ethenyl, propenyl, butenyl, 1-methyl-2-buten-1-yl, and the like. Representative alkynyl groups include, but are not limited to, ethynyl, 2-propynyl (propargyl), 1-propynyl and the like.
The term “alicyclic”, as used herein, refers to compounds which combine the properties of aliphatic and cyclic compounds and include but are not limited to cyclic, or polycyclic aliphatic hydrocarbons and bridged cycloalkyl compounds, which are optionally substituted with one or more functional groups. As will be appreciated by one of ordinary skill in the art, “alicyclic” is intended herein to include, but is not limited to, cycloalkyl, cycloalkenyl, and cycloalkynyl moieties, which are optionally substituted with one or more functional groups. Illustrative alicyclic groups thus include, but are not limited to, for example, cyclopropyl, —CH 2 -cyclopropyl, cyclobutyl, —CH 2 -cyclobutyl, cyclopentyl, —CH 2 -cyclopentyl-n, cyclohexyl, —CH 2 -cyclohexyl, cyclohexenylethyl, cyclohexanylethyl, norborbyl moieties and the like, which again, may bear one or more substituents.
The term “alkoxy” (or “alkyloxy”), or “thioalkyl” as used herein refers to an alkyl group, as previously defined, attached to the parent molecular moiety through an oxygen atom or through a sulfur atom. In certain embodiments, the alkyl group contains 1-20 aliphatic carbon atoms. In certain other embodiments, the alkyl group contains 1-10 aliphatic carbon atoms. In yet other embodiments, the alkyl, alkenyl, and alkynyl groups employed in the invention contain 1-8 aliphatic carbon atoms. In still other embodiments, the alkyl group contains 1-6 aliphatic carbon atoms. In yet other embodiments, the alkyl group contains 1-4 aliphatic carbon atoms. Examples of alkoxy, include but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, tert-butoxy, neopentoxy and n-hexoxy. Examples of thioalkyl include, but are not limited to, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, and the like.
The term “alkylamino” refers to a group having the structure —NHR′ wherein R′ is alkyl, as defined herein. The term “aminoalkyl” refers to a group having the structure NH 2 R′—, wherein R′ is alkyl, as defined herein. In certain embodiments, the alkyl group contains 1-20 aliphatic carbon atoms. In certain other embodiments, the alkyl group contains 1-10 aliphatic carbon atoms. In yet other embodiments, the alkyl, alkenyl, and alkynyl groups employed in the invention contain 1-8 aliphatic carbon atoms. In still other embodiments, the alkyl group contains 1-6 aliphatic carbon atoms. In yet other embodiments, the alkyl group contains 1-4 aliphatic carbon atoms. Examples of alkylamino include, but are not limited to, methylamino, ethylamino, iso-propylamino and the like.
Some examples of substituents of the above-described aliphatic (and other) moieties of compounds of the invention include, but are not limited to aliphatic; heteroaliphatic; aryl; heteroaryl; alkylaryl; alkylheteroaryl; alkoxy; aryloxy; heteroalkoxy; heteroaryloxy; alkylthio; arylthio; heteroalkylthio; heteroarylthio; F; Cl; Br; I; —OH; —NO 2 ; —CN; —CF 3 ; —CH 2 CF 3 ; —CHCl 2 ; —CH 2 OH; —CH 2 CH 2 OH; —CH 2 NH 2 ; —CH 2 SO 2 CH 3 ; —C(O)R x ; —CO 2 (R x ); —CON(R x ) 2 ; —OC(O)R x ; —OCO 2 R x ; —OCON(R x ) 2 ; —N(R x ) 2 ; —S(O) 2 R x ; —NR x (CO)R x wherein each occurrence of R x independently includes, but is not limited to, aliphatic, alycyclic, heteroaliphatic, heterocyclic, aryl, heteroaryl, alkylaryl, or alkylheteroaryl, wherein any of the aliphatic, heteroaliphatic, alkylaryl, or alkylheteroaryl substituents described above and herein may be substituted or unsubstituted, branched or unbranched, cyclic or acyclic, and wherein any of the aryl or heteroaryl substituents described above and herein may be substituted or unsubstituted. Additional examples of generally applicable substituents are illustrated by the specific embodiments shown in the Examples that are described herein.
In general, the term “aromatic moiety”, as used herein, refers to a stable mono-or polycyclic, unsaturated moiety having preferably 3-14 carbon atoms, each of which may be substituted or unsubstituted. In certain embodiments, the term “aromatic moiety” refers to a planar ring having p-orbitals perpendicular to the plane of the ring at each ring atom and satisfying the Huckel rule where the number of pi electrons in the ring is (4n+2) wherein n is an integer. A mono-or polycyclic, unsaturated moiety that does not satisfy one or all of these criteria for aromaticity is defined herein as “non-aromatic”, and is encompassed by the term “alicyclic”.
In general, the term “heteroaromatic moiety”, as used herein, refers to a stable mono-or polycyclic, unsaturated moiety having preferably 3-14 carbon atoms, each of which may be substituted or unsubstituted; and comprising at least one heteroatom selected from O, S and N within the ring (i.e., in place of a ring carbon atom). In certain embodiments, the term “heteroaromatic moiety” refers to a planar ring comprising at least on heteroatom, having p-orbitals perpendicular to the plane of the ring at each ring atom, and satisfying the Huckel rule where the number of pi electrons in the ring is (4n+2) wherein n is an integer.
It will also be appreciated that aromatic and heteroaromatic moieties, as defined herein may be attached via an alkyl or heteroalkyl moiety and thus also include -(alkyl)aromatic, -(heteroalkyl)aromatic, -(heteroalkyl)heteroaromatic, and -(heteroalkyl)heteroaromatic moieties. Thus, as used herein, the phrases “aromatic or heteroaromatic moieties” and “aromatic, heteroaromatic, -(alkyl)aromatic, -(heteroalkyl)aromatic, -(heteroalkyl)heteroaromatic, and -(heteroalkyl)heteroaromatic” are interchangeable. Substituents include, but are not limited to, any of the previously mentioned substituents, i.e., the substituents recited for aliphatic moieties, or for other moieties as disclosed herein, resulting in the formation of a stable compound.
The term “aryl”, as used herein, does not differ significantly from the common meaning of the term in the art, and refers to an unsaturated cyclic moiety comprising at least one aromatic ring. In certain embodiments, “aryl” refers to a mono-or bicyclic carbocyclic ring system having one or two aromatic rings including, but not limited to, phenyl, naphthyl, tetrahydronaphthyl, indanyl, indenyl and the like.
The term “heteroaryl”, as used herein, does not differ significantly from the common meaning of the term in the art, and refers to a cyclic aromatic radical having from five to ten ring atoms of which one ring atom is selected from S, O and N; zero, one or two ring atoms are additional heteroatoms independently selected from S, O and N; and the remaining ring atoms are carbon, the radical being joined to the rest of the molecule via any of the ring atoms, such as, for example, pyridyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, isooxazolyl, thiadiazolyl, oxadiazolyl, thiophenyl, furanyl, quinolinyl, isoquinolinyl, and the like.
It will be appreciated that aryl and heteroaryl groups (including bicyclic aryl groups) can be unsubstituted or substituted, wherein substitution includes replacement of one or more of the hydrogen atoms thereon independently with any one or more of the following moieties including, but not limited to: aliphatic; alicyclic; heteroaliphatic; heterocyclic; aromatic; heteroaromatic; aryl; heteroaryl; alkylaryl; heteroalkylaryl; alkylheteroaryl; heteroalkylheteroaryl; alkoxy; aryloxy; heteroalkoxy; heteroaryloxy; alkylthio; arylthio; heteroalkylthio; heteroarylthio; F; Cl; Br; I; —OH; —NO 2 ; —CN; —CF 3 ; —CH 2 CF 3 ; —CHCl 2 ; —CH 2 OH; —CH 2 CH 2 OH; —CH 2 NH 2 ; —CH 2 SO 2 CH 3 ; —C(O)R x ; —CO 2 (R x ); —CON(R x ) 2 ; —OC(O)R x ; —OCO 2 R x ; —OCON(R x ) 2 ; —N(R x ) 2 ; —S(O)R x ; —S(O) 2 R x ; —NR x (CO)R x wherein each occurrence of R x , independently includes, but is not limited to, aliphatic, alicyclic, heteroaliphatic, heterocyclic, aromatic, heteroaromatic, aryl, heteroaryl, alkylaryl, allylheteroaryl, heteroalkylaryl or heteroalkylheteroaryl, wherein any of the aliphatic, alicyclic, heteroaliphatic, heterocyclic, alkylaryl, or alkylheteroaryl substituents described above and herein may be substituted or unsubstituted, branched or unbranched, saturated or unsaturated, and wherein any of the aromatic, heteroaromatic, aryl, heteroaryl, -(alkyl)aryl or -(alkyl)heteroaryl substituents described above and herein may be substituted or unsubstituted. Additionally, it will be appreciated, that any two adjacent groups taken together may represent a 4, 5, 6, or 7-membered substituted or unsubstituted alicyclic or heterocyclic moiety. Additional examples of generally applicable substituents are illustrated by the specific embodiments shown in the Examples that are described herein.
The term “cycloalkyl”, as used herein, refers specifically to groups having three to seven, preferably three to ten carbon atoms. Suitable cycloalkyls include, but are not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and the like, which, as in the case of aliphatic, alicyclic, heteroaliphatic or heterocyclic moieties, may optionally be substituted with substituents including, but not limited to aliphatic; alicyclic; heteroaliphatic; heterocyclic; aromatic; heteroaromatic; aryl; heteroaryl; alkylaryl; heteroalkylaryl; alkylheteroaryl; heteroalkylheteroaryl; alkoxy; aryloxy; heteroalkoxy; heteroaryloxy; alkylthio; arylthio; heteroalkylthio; heteroarylthio; F; Cl; Br; I; —OH; —NO 2 ; —CN; —CF 3 ; —CH 2 CF 3 ; —CHCl 2 ; —CH 2 OH; —CH 2 CH 2 OH; —CH 2 NH 2 ; —CH 2 SO 2 CH 3 ; —C(O)R x ; —CO 2 (R x ); —CON(R x ) 2 ; —OC(O)R x ; —OCO 2 R x ; —OCON(R x ) 2 ; —N(R x ) 2 ; —S(O) 2 R x ; —NR x (CO)R x wherein each occurrence of R x independently includes, but is not limited to, aliphatic, alicyclic, heteroaliphatic, heterocyclic, aromatic, heteroaromatic, aryl, heteroaryl, alkylaryl, alkylheteroaryl, heteroalkylaryl or heteroalkylheteroaryl, wherein any of the aliphatic, alicyclic, heteroaliphatic, heterocyclic, alkylaryl, or alkylheteroaryl substituents described above and herein may be substituted or unsubstituted, branched or unbranched, saturated or usaturated, and wherein any of the aromatic, heteroaromatic, aryl or heteroaryl substituents described above and herein may be substituted or unsubstituted. Additional examples of generally applicable substituents are illustrated by the specific embodiments shown in the Examples that are described herein.
The term “heteroaliphatic”, as used herein, refers to aliphatic moieties in which one or more carbon atoms in the main chain have been substituted with a heteroatom. Thus, a heteroaliphatic group refers to an aliphatic chain which contains one or more oxygen, sulfur, nitrogen, phosphorus or silicon atoms, e.g., in place of carbon atoms. Heteroaliphatic moieties may be linear or branched, and saturated or unsaturated. In certain embodiments, heteroaliphatic moieties are substituted by independent replacement of one or more of the hydrogen atoms thereon with one or more moieties including, but not limited to aliphatic; alicyclic; heteroaliphatic; heterocyclic; aromatic; heteroaromatic; aryl; heteroaryl; alkylaryl; alkylheteroaryl; alkoxy; aryloxy; heteroalkoxy; heteroaryloxy; alkylthio; arylthio; heteroalkylthio; heteroarylthio; F; Cl; Br; I; —OH; —NO 2 ; —CN; —CF 3 ; —CH 2 CF 3 ; —CHCl 2 ; —CH 2 OH; —CH 2 CH 2 OH; —CH 2 NH 2 ; —CH 2 SO 2 CH 3 ; —C(O)R x ; —CO 2 (R x ); —CON(R x ) 2 ; —OC(O)R x ; —OCO 2 R x ; —OCON(R x ) 2 ; —N(R x ) 2 ; —S(O) 2 R x ; —NR x (CO)R x , wherein each occurrence of R x independently includes, but is not limited to, aliphatic, alicyclic, heteroaliphatic, heterocyclic, aromatic, heteroaromatic, aryl, heteroaryl, alkylaryl, alkylheteroaryl, heteroalkylaryl or heteroalkylheteroaryl, wherein any of the aliphatic, alicyclic, heteroaliphatic, heterocyclic, alkylaryl, or alkylheteroaryl substituents described above and herein may be substituted or unsubstituted, branched or unbranched, saturated or unsaturated, and wherein any of the aromatic, heteroaromatic, aryl or heteroaryl substituents described above and herein may be substituted or unsubstituted. Additional examples of generally applicable substituents are illustrated by the specific embodiments shown in the Examples that are described herein. The term “heterocycloalkyl”, “heterocycle” or “heterocyclic”, as used herein, refers to compounds which combine the properties of heteroaliphatic and cyclic compounds and include, but are not limited to, saturated and unsaturated mono-or polycyclic cyclic ring systems having 5-16 atoms wherein at least one ring atom is a heteroatom selected from O, S and N (wherein the nitrogen and sulfur heteroatoms may be optionally be oxidized), wherein the ring systems are optionally substituted with one or more functional groups, as defined herein. In certain embodiments, the term “heterocycloalkyl”, “heterocycle” or “heterocyclic” refers to a non-aromatic 5-, 6-, or 7-membered ring or a polycyclic group wherein at least one ring atom is a heteroatom selected from O, S and N (wherein the nitrogen and sulfur heteroatoms may be optionally be oxidized), including, but not limited to, a bi-or tri-cyclic group, comprising fused six-membered rings having between one and three heteroatoms independently selected from oxygen, sulfur and nitrogen, wherein (i) each 5-membered ring has 0 to 2 double bonds, each 6-membered ring has 0 to 2 double bonds and each 7-membered ring has 0 to 3 double bonds, (ii) the nitrogen and sulfur heteroatoms may be optionally be oxidized, (iii) the nitrogen heteroatom may optionally be quaternized, and (iv) any of the above heterocyclic rings may be fused to an aryl or heteroaryl ring. Representative heterocycles include, but are not limited to, heterocycles such as furanyl, thiofuranyl, pyranyl, pyrrolyl, thienyl, pyrrolidinyl, pyrazolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, piperidinyl, piperazinyl, oxazolyl, oxazolidinyl, isooxazolyl, isoxazolidinyl, dioxazolyl, thiadiazolyl, oxadiazolyl, tetrazolyl, triazolyl, thiatriazolyl, oxatriazolyl, thiadiazolyl, oxadiazolyl, morpholinyl, thiazolyl, thiazolidinyl, isothiazolyl, isothiazolidinyl, dithiazolyl, dithiazolidinyl, tetrahydrofuryl, and benzofused derivatives thereof. In certain embodiments, a “substituted heterocycle, or heterocycloalkyl or heterocyclic” group is utilized and as used herein, refers to a heterocycle, or heterocycloalkyl or heterocyclic group, as defined above, substituted by the independent replacement of one, two or three of the hydrogen atoms thereon with but are not limited to aliphatic; alicyclic; heteroaliphatic; heterocyclic; aromatic; heteroaromatic; aryl; heteroaryl; alkylaryl; heteroalkylaryl; alkylheteroaryl; heteroalkylheteroaryl; alkoxy; aryloxy; heteroalkoxy; heteroaryloxy; alkylthio; arylthio; heteroalkylthio; heteroarylthio; F; Cl; Br; I; —OH; —NO 2 ; —CN; —CF 3 ; —CH 2 CF 3 ; —CHCl 2 ; —CH 2 OH; —CH 2 CH 2 OH; —CH 2 NH 2 ; —CH 2 SO 2 CH 3 ; —C(O)R x ; —CO 2 (R x ); —CON(R x ) 2 ; —OC(O)R x ; —OCO 2 R x ; —OCON(R x ) 2 ; —N(R x ) 2 ; —S(O) 2 R x ; —NR x (CO)R x wherein each occurrence of R x independently includes, but is not limited to, aliphatic, alicyclic, heteroaliphatic, heterocyclic, aromatic, heteroaromatic, aryl, heteroaryl, alkylaryl, alkylheteroaryl, heteroalkylaryl or heteroalkylheteroaryl, wherein any of the aliphatic, alicyclic, heteroaliphatic, heterocyclic, alkylaryl, or alkylheteroaryl substituents described above and herein may be substituted or unsubstituted, branched or unbranched, saturated or unsaturated, and wherein any of the aromatic, heteroaromatic, aryl or heteroaryl substitutents described above and herein may be substituted or unsubstituted. Additional examples or generally applicable substituents are illustrated by the specific embodiments shown in the Examples, which are described herein.
Additionally, it will be appreciated that any of the alicyclic or heterocyclic moieties described above and herein may comprise an aryl or heteroaryl moiety fused thereto. Additional examples of generally applicable substituents are illustrated by the specific embodiments shown in the Examples that are described herein. The terms “halo” and “halogen” as used herein refer to an atom selected from fluorine, chlorine, bromine and iodine.
The terms “halo” and “halogen” as used herein refer to an atom selected from fluorine, chlorine, bromine, and iodine.
The term “haloalkyl” denotes an alkyl group, as defined above, having one, two, or three halogen atoms attached thereto and is exemplified by such groups as chloromethyl, bromoethyl, trifluoromethyl, and the like.
The term “amino”, as used herein, refers to a primary (—NH 2 ), secondary (—NHR x ), tertiary (—NR x R y ) or quaternary (—N + R x R y R z ) amine, where R x , R y and R z are independently an aliphatic, alicyclic, heteroaliphatic, heterocyclic, aromatic or heteroaromatic moiety, as defined herein. Examples of amino groups include, but are not limited to, methylamino, dimethylamino, ethylamino, diethylamino, diethylaminocarbonyl, methylethylamino, iso-propylamino, piperidino, trimethylamino, and propylamino.
The term “alkylidene”, as used herein, refers to a substituted or unsubstituted, linear or branched saturated divalent radical consisting solely of carbon and hydrogen atoms, having from one to n carbon atoms, having a free valence “−” at both ends of the radical.
The term “alkenylidene”, as used herein, refers to a substituted or unsubstituted, linear or branched unsaturated divalent radical consisting solely of carbon and hydrogen atoms, having from two to n carbon atoms, having a free valence “−” at both ends of the radical, and wherein the unsaturation is present only as double bonds and wherein a double bond can exist between the first carbon of the chain and the rest of the molecule.
The term “alkynylidene”, as used herein, refers to a substituted or unsubstituted, linear or branched unsaturated divalent radical consisting solely of carbon and hydrogen atoms, having from two to n carbon atoms, having a free valence “−” at both ends of the radical, and wherein the unsaturation is present only as triple bonds and wherein a triple bond can exist between the first carbon of the chain and the rest of the molecule.
Unless otherwise indicated, as used herein, the terms “alkyl”, “alkenyl”, “alkynyl”, “heteroalkyl”, “heteroalkenyl”, “heteroalkynyl”, “alkylidene”, alkenylidene”, -(alkyl)aryl, -(heteroalkyl)aryl, -(heteroalkyl)aryl, -(heteroalkyl)heteroaryl, and the like encompass substituted and unsubstituted, and linear and branched groups. Similarly, the terms “aliphatic”, “heteroaliphatic”, and the like encompass substituted and unsubstituted, saturated and unsaturated, and linear and branched groups. Similarly, the terms “cycloalkyl”, “heterocycle”, “heterocyclic”, and the like encompass substituted and unsubstituted, and saturated and unsaturated groups. Additionally, the terms “cycloalkenyl”, “cycloalkynyl”, “heterocycloalkenyl”, “heterocycloalkynyl”, “aromatic”, “heteroaromatic, “aryl”, “heteroaryl” and the like encompass both substituted and unsubstituted groups.
The phrase, “pharmaceutically acceptable derivative”, as used herein, denotes any pharmaceutically acceptable salt, ester, or salt of such ester, of such compound, or any other adduct or derivative which, upon administration to a patient, is capable of providing (directly or indirectly) a compound as otherwise described herein, or a metabolite or residue thereof. Pharmaceutically acceptable derivatives thus include among others pro-drugs. A pro-drug is a derivative of a compound, usually with significantly reduced pharmacological activity, which contains an additional moiety, which is susceptible to removal in vivo yielding the parent molecule as the pharmacologically active species. An example of a pro-drug is an ester, which is cleaved in vivo to yield a compound of interest. Pro-drugs of a variety of compounds, and materials and methods for derivatizing the parent compounds to create the pro-drugs, are known and may be adapted to the present invention. Pharmaceutically acceptable derivatives also include “reverse pro-drugs.” Reverse pro-drugs, rather than being activated, are inactivated upon absorption. For example, as discussed herein, many of the ester-containing compounds of the invention are biologically active but are inactivated upon exposure to certain physiological environments such as a blood, lymph, serum, extracellular fluid, etc. which contain esterase activity. The biological activity of reverse pro-drugs and pro-drugs may also be altered by appending a functionality onto the compound, which may be catalyzed by an enzyme. Also, included are oxidation and reduction reactions, including enzyme-catalyzed oxidation and reduction reactions. Certain exemplary pharmaceutical compositions and pharmaceutically acceptable derivatives will be discussed in more detail herein below.
The term “linker,” as used herein, refers to a chemical moiety utilized to attach one part of a compound of interest to another part of the compound. Exemplary linkers are described herein.
Unless indicated otherwise, the terms defined below have the following meanings:
“Compound”: The term “compound” or “chemical compound” as used herein can include organometallic compounds, organic compounds, metals, transitional metal complexes, and small molecules. In certain preferred embodiments, polynucleotides are excluded from the definition of compounds. In other preferred embodiments, polynucleotides and peptides are excluded from the definition of compounds. In a particularly preferred embodiment, the term compounds refers to small molecules (e.g., preferably, non-peptidic and non-oligomeric) and excludes peptides, polynucleotides, transition metal complexes, metals, and organometallic compounds.
“Small Molecule”: As used herein, the term “small molecule” refers to a non-peptidic, non-oligomeric organic compound either synthesized in the laboratory or found in nature. Small molecules, as used herein, can refer to compounds that are “natural product-like”, however, the term “small molecule” is not limited to “natural product-like” compounds. Rather, a small molecule is typically characterized in that it contains several carbon-carbon bonds, and has a molecular weight of less than 2000 g/mol, preferably less than 1500 g/mol, although this characterization is not intended to be limiting for the purposes of the present invention. Examples of “small molecules” that occur in nature include, but are not limited to, taxol, dynemicin, and rapamycin. Examples of “small molecules” that are synthesized in the laboratory include, but are not limited to, compounds described in Tan et al., (“Stereoselective Synthesis of over Two Million Compounds Having Structural Features Both Reminiscent of Natural Products and Compatible with Miniaturized Cell-Based Assays” J. Am. Chem. Soc. 120:8565, 1998; incorporated herein by reference). In certain other preferred embodiments, natural-product-like small molecules are utilized.
“Natural Product-Like Compound”: As used herein, the term “natural product-like compound” refers to compounds that are similar to complex natural products which nature has selected through evolution. Typically, these compounds contain one or more stereocenters, a high density and diversity of functionality, and a diverse selection of atoms within one structure. In this context, diversity of functionality can be defined as varying the topology, charge, size, hydrophilicity, hydrophobicity, and reactivity to name a few, of the functional groups present in the compounds. The term, “high density of functionality”, as used herein, can preferably be used to define any molecule that contains preferably three or more latent or active diversifiable functional moieties. These structural characteristics may additionally render the inventive compounds functionally reminiscent of complex natural products, in that they may interact specifically with a particular biological receptor, and thus may also be functionally natural product-like.
“Metal chelator”: As used herein, the term “metal chelator” refers to any molecule or moiety that is capable of forming a complex (i.e., “chelates”) with a metal ion. In certain exemplary embodiments, a metal chelator refers to to any molecule or moiety that “binds” to a metal ion, in solution, making it unavailable for use in chemical/enzymatic reactions. In certain embodiments, the solution comprises aqueous environments under physiological conditions. Examples of metal ions include, but are not limited to, Ca 2+ , Fe 3+ , Zn 2+ , Na + , etc. In certain embodiments, the metal chelator binds Zn 2+ . In certain embodiments, molecules of moieties that precipitate metal ions are not considered to be metal chelators.
As used herein the term “biological sample” includes, without limitation, cell cultures or extracts thereof; biopsied material obtained from an animal (e.g., mammal) or extracts thereof; and blood, saliva, urine, feces, semen, tears, or other body fluids or extracts thereof. For example, the term “biological sample” refers to any solid or fluid sample obtained from, excreted by or secreted by any living organism, including single-celled micro-organisms (such as bacteria and yeasts) and multicellular organisms (such as plants and animals, for instance a vertebrate or a mammal, and in particular a healthy or apparently healthy human subject or a human patient affected by a condition or disease to be diagnosed or investigated). The biological sample can be in any form, including a solid material such as a tissue, cells, a cell pellet, a cell extract, cell homogenates, or cell fractions; or a biopsy, or a biological fluid. The biological fluid may be obtained from any site (e.g., blood, saliva (or a mouth wash containing buccal cells), tears, plasma, serum, urine, bile, cerebrospinal fluid, amniotic fluid, peritoneal fluid, and pleural fluid, or cells therefrom, aqueous or vitreous humor, or any bodily secretion), a transudate, an exudate (e.g. fluid obtained from an abscess or any other site of infection or inflammation), or fluid obtained from a joint (e.g. a normal joint or a joint affected by disease such as rheumatoid arthritis, osteoarthritis, gout or septic arthritis). The biological sample can be obtained from any organ or tissue (including a biopsy or autopsy specimen) or may comprise cells (whether primary cells or cultured cells) or medium conditioned by any cell, tissue or organ. Biological samples may also include sections of tissues such as frozen sections taken for histological purposes. Biological samples also include mixtures of biological molecules including proteins, lipids, carbohydrates and nucleic acids generated by partial or complete fractionation of cell or tissue homogenates. Although the sample is preferably taken from a human subject, biological samples may be from any animal, plant, bacteria, virus, yeast, etc. The term animal, as used herein, refers to humans as well as non-human animals, at any stage of development, including, for example, mammals, birds, reptiles, amphibians, fish, worms and single cells. Cell cultures and live tissue samples are considered to be pluralities of animals. In certain exemplary embodiments, the non-human animal is a mammal (e.g., a rodent, a mouse, a rat, a rabbit, a monkey, a dog, a cat, a sheep, cattle, a primate, or a pig). An animal may be a transgenic animal or a human clone. If desired, the biological sample may be subjected to preliminary processing, including preliminary separation techniques.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 includes a table of esterases found in human and mouse plasma.
FIG. 2 shows the design of a reverse pro-drug version of SAHA-SAHP.
FIG. 3 illustrates the stability of SAHA (with an amide) in PBS.
FIG. 4 illustrates the stability of SAHA in serum.
FIG. 5 shows the stability of SAHP (ester instead of amdie) in PBS.
FIG. 6 shows the degradation of SAHP in serum. In less than 15 minutes, SAHP is completely degraded.
FIG. 7 shows a more detailed study of the degradation of SAHP in serum. In less than 2 minutes, SAHP is completely degraded into phenol and the corresponding carboxylic acid.
FIG. 8 shows the degradation of SAHP by human serum under various conditions.
FIG. 9 shows the degradation of SAHP by recombinant paraoxonase.
FIG. 10 shows the degradation of SAHP in RPMI media with 10% FBS.
FIG. 11 shows the effect of SAHA v. SAHP on lysine acetylation.
FIG. 12 shows the stability of SAHP in an olive oil/acetone formulation for murine model.
FIG. 13 is an exemplary synthetic scheme for preparing SAHP.
FIG. 14 . Interleukin-7 is a growth factor for T-cell development, in particular the gamma-delta subset. Transgenic mice overexpressing IL-7 in keratinocytes were developed by the laboratories of Thomas Kupper and Benjamin Rich, using a tissue-specific keratin-14 promoter element. These mice have been reported to develop a characteristic lymphoproliferative skin disease grossly and histologically similar to human cutaneous T-cell lymphoma (CTCL). Transformed lymphocytes derived from involved skin were passaged ex vivo and injected into syngeneic (non-transgenic) mice. After fourteen days, these mice develop a homogeneous lymphoproliferative disease. Two cohorts of five mice were included in a prospective study of topical, daily suberoyl hydroxamic acid phenyl ester (SAHP, also known as SHAPE) versus vehicle control. After fourteen days of therapy, mice were sacrificed and the treated region was dissected for histopathologic examination. In SHAPE-treated mice, hematoxylin-eosin staining demonstrates a marked reduction in lymphomatous infiltration within the treated window. Vehicle control mice failed to demonstrate a cytotoxic response.
FIG. 15 shows the pharmacodynamic effect of SAHP treatment as assessed using immunohistochemical staining for acetylated histones compared to vehicle treated controls. In SAHP-treated mice, ACH3K18 staining demonstrates hyperacetylated histone staining at the margin of compound treatment, with absent nuclear staining in the region of drug response. Vehicle control mice failed to demonstrate an increase in histone hyperacetylation.
DETAILED DESCRIPTION OF THE INVENTION
As discussed above, there remains a need for the development of novel histone deacetylase inhibitors. The present invention provides novel compounds of general formula (I), and methods for the synthesis thereof, which compounds are useful as inhibitors of histone deacetylases, and thus are useful for the treatment of proliferative diseases, particularly proliferative or other disorders associated with the skin and/or hair. In particular, the inventive compounds comprise an ester linkage. The ester linkage is preferably sensitive to esterase cleavage; therefore, when the compound is contacted with an esterase it is deactivated.
Compounds of the Invention
As discussed above, the present invention provides a novel class of compounds useful for the treatment of cancer and other proliferative conditions related thereto. In certain embodiments, the compounds of the present invention are useful as inhibitors of histone deacetylases and thus are useful as anticancer agents, and thus may be useful in the treatment of cancer, by effecting tumor cell death or inhibiting the growth of tumor cells. In certain exemplary embodiments, the inventive anticancer agents are useful in the treatment of cancers and other proliferative disorders, including, but not limited to breast cancer, cervical cancer, colon and rectal cancer, leukemia, lung cancer, melanoma, multiple myeloma, non-Hodgkin's lymphoma, ovarian cancer, pancreatic cancer, prostate cancer, and gastric cancer, to name a few. In certain embodiments, the inventive anticancer agents are active against leukemia cells and melanoma cells, and thus are useful for the treatment of leukemias (e.g., myeloid, lymphocytic, myelocytic and lymphoblastic leukemias) and malignant melanomas. In certain embodiments, the inventive compounds are active against cutaneous T-cell lymphoma. Additionally, as described above and in the exemplification, the inventive compounds may also be useful in the treatment of protozoal infections. In certain exemplary embodiments, the compounds of the invention are useful for disorders resulting from histone deacetylation activity. In certain embodiments, the compounds are useful for skin disorders. Exemplary skin disorders that may be treated using the inventive compounds include cutaneous T-cell lymphoma (CTCL), skin cancers (e.g., squamous cell carcinoma, basal cell carcinoma, malignant melanoma, etc.), psoriasis, hair loss, dermatitis, neurofibromatosis, disorders associated with skin hyperpigmentation, etc.
Compounds of this invention comprise those, as set forth above and described herein, and are illustrated in part by the various classes, subgenera and species disclosed elsewhere herein.
In general, the present invention provides compounds having the general structure (I):
and pharmaceutically acceptable salts and derivatives thereof;
wherein
A comprises a functional group that inhibits histone deacetylase;
L is a linker moiety; and
Ar is a substituted or unsubstituted aryl or heteroaryl moiety; substituted or unsustituted, branched or unbranched arylaliphatic or heteroarylaliphatic moiety; a substituted or unsubstituted cyclic or heterocyclic moiety; substituted or unsustituted, branched or unbranched cyclicaliphatic or heterocyclicaliphatic moiety.
In certain embodiments, A comprises a metal chelating functional group. For example, A comprises a Zn 2+ chelating group. In certain embodiments, A comprises a functional group selected group consisting of:
In certain embodiments, A comprises hydroxamic acid
or a salt thereof. In other embodiments, A comprises the formula:
In certain particular embodiments, A comprises the formula:
In other embodiments, A comprises a carboxylic acid (—CO 2 H). In other embodiments, A
comprises an o-aminoanilide
In other embodiments, A comprises an o-hydroxyanilide
In yet other embodiments, A comprises a thiol (—SH).
In certain embodiments, Ar is arylaliphatic. In other embodiments, Ar is heteroarylaliphatic. In certain embodiments, Ar is a substituted or unsubstituted aryl moiety. In certain embodiments, Ar is a monocylic, substituted or unsubstituted aryl moiety, preferably a five-or six-membered aryl moiety. In other embodiments, Ar is a bicyclic, substituted or unsubstituted aryl moiety. In still other embodiments, Ar is a tricyclic, substituted or unsubstituted aryl moiety. In certain embodiments, Ar is a substituted or unsubstituted phenyl moiety. In certain embodiments, Ar is an unsubstituted phenyl moiety. In other embodiments, Ar is a substituted phenyl moiety. In certain embodiments, Ar is a monosubstituted phenyl moiety. In certain particular embodiments, Ar is an ortho-substituted Ar moiety. In certain particular embodiments, Ar is an meta-substituted Ar moiety. In certain particular embodiments, Ar is an para-substituted Ar moiety. In certain embodiments, Ar is a disubstituted phenyl moiety. In certain embodiments, Ar is a trisubstituted phenyl moiety. In certain embodiments, Ar is a tetrasubstituted phenyl moiety. In certain embodiments, Ar is a substituted or unsubstituted cyclic or heterocyclic.
In certain embodiments, Ar is a substituted or unsubstituted heteroaryl moiety. In certain embodiments, Ar is a monocylic, substituted or unsubstituted heteroaryl moiety, preferably a five-or six-membered heteroaryl moiety. In other embodiments, Ar is a bicyclic, substituted or unsubstituted heteroaryl moiety. In still other embodiments, Ar is a tricyclic, substituted or unsubstituted heteroaryl moiety. In certain embodiments, Ar comprises N, S, or O. In certain embodiments, Ar comprises at least one N. In certain embodiments, Ar comprises at least two N.
In certain embodiments, Ar is:
wherein
n is an integer between 1 and 5, inclusive; preferably, between 1 and 3, inclusive; more preferably, 1 or 2;
R 1 is hydrogen; halogen; cyclic or acyclic, substituted or unsubstituted, branched or unbranched aliphatic; cyclic or acyclic, substituted or unsubstituted, branched or unbranched heteroaliphatic; substituted or unsubstituted, branched or unbranched acyl; substituted or unsubstituted, branched or unbranched aryl; substituted or unsubstituted, branched or unbranched heteroaryl; —OR A ; —C(═O)R A ; —CO 2 R A ; —CN; —SCN; —SR A ; —SOR A ; —SO 2 R A ; —NO 2 ; —N(R A ) 2 ; —NHR A ; —NHC(O)R A ; or —C(R A ) 3 ; wherein each occurrence of R A is independently a hydrogen, a protecting group, an aliphatic moiety, a heteroaliphatic moiety, an acyl moiety; an aryl moiety; a heteroaryl moiety; alkoxy; aryloxy; alkylthio; arylthio; amino, alkylamino, dialkylamino, heteroaryloxy; or heteroarylthio moiety. In certain embodiments, Ar is
In other embodiments, Ar is
In yet other embodiments, Ar is
In certain embodiments, R 1 is —N(R A ) 2 , wherein R A is hydrogen or C 1 -C 6 alkyl. In certain embodiments, R 1 is —OR A , wherein R A is hydrogen or C 1 -C 6 alkyl. In certain particular embodiments, R 1 is —OMe. In certain embodiments, R 1 is branched or unbranched acyl. In certain embodiments, R 1 is —O(═O)OR A . In certain embodiments, R 1 is —C(═O)OR A , wherein R A is hydrogen or C 1 -C 6 alkyl. In certain embodiments, R 1 is —C(═O)NH 2 . In certain embodiments, R 1 is —NHC(═O)R A . In certain embodiments, R 1 is —NHC(═O)R A , wherein R A is hydrogen or C 1 -C 6 alkyl. In certain embodiments, R 1 is halogen. In certain embodiments, R 1 is C 1 -C 6 alkyl.
In certain particular embodiments, Ar is a substituted phenyl moiety of formula:
In certain embodiments, Ar is chosen from one of the following:
wherein
n is an integer between 1 and 4, inclusive; preferably, between 1 and 3, inclusive; more preferably, 1 or 2;
R 1 is hydrogen; halogen; cyclic or acyclic, substituted or unsubstituted, branched or unbranched aliphatic; cyclic or acyclic, substituted or unsubstituted, branched or unbranched heteroaliphatic; substituted or unsubstituted, branched or unbranched acyl; substituted or unsubstituted, branched or unbranched aryl; substituted or unsubstituted, branched or unbranched heteroaryl; —OR A ; —C(═O)R A ; —CO 2 R A ; —CN; —SCN; —SR A ; —SOR A ; —SO 2 R A ; —NO 2 ; —N(R A ) 2 ; —NHR A ; —NHC(O)R A ; or —C(R A ) 3 ; wherein each occurrence of R A is independently a hydrogen, a protecting group, an aliphatic moiety, a heteroaliphatic moiety, an acyl moiety; an aryl moiety; a heteroaryl moiety; alkoxy; aryloxy; alkylthio; arylthio; amino, alkylamino, dialkylamino, heteroaryloxy; or heteroarylthio moiety.
In certain embodiments, Ar is chosen from one of the following:
Any of the above bicyclic ring system may be substituted with up to seven R x , substituents as defined above.
In certain embodiments, L is a substituted or unsubstituted, cyclic or acyclic, branched or unbranched aliphatic moiety; a substituted or unsubstituted, cyclic or acyclic, branched or unbranched heteroaliphatic moiety; a substituted or unsubstituted aryl moiety; a substituted or unsubstituted heteroaryl moiety. In certain embodiments, L is a substituted or unsubstituted, cyclic or acyclic, branched or unbranched aliphatic moiety. In certain embodiments, L is C 1 -C 20 alkylidene, preferably C 1 to C 12 alkylidene, more preferably C 4 -C 7 alkylidene. In certain embodiments, L is C 1 -C 20 alkenylidene, preferably C 1 to C 12 alkenylidene, more preferably C 4 -C 7 alkenylidene. In certain embodiments, L is C 1 -C 20 alkynylidene, preferably C 1 to C 12 alkynylidene, more preferably C 4 -C 7 alkynylidene. In certein embodiments, L is a a substituted or unsubstituted, cyclic or acyclic, branched or unbranched heteroaliphatic moiety. In certain embodiments, L comprises a cyclic ring system, wherein the rings may be aryl, heteroaryl, non-aromatic carbocyclic, or non-aromatic heterocyclic. In still other embodiments, L comprises a substituted or unsubstituted heteroaryl moiety. In certain particular embodiments, L comprises a phenyl ring. In certain embodiments, L comprises multiple phenyl rings (e.g., one, two, three, or four phenyl rings).
In certain embodiments, L is
wherein n is an integer between 1 and 4, inclusive; preferably, between 1 and 3, inclusive; more preferably, 1 or 2; and R 1 is is hydrogen; halogen; cyclic or acyclic, substituted or unsubstituted, branched or unbranched aliphatic; cyclic or acyclic, substituted or unsubstituted, branched or unbranched heteroaliphatic; substituted or unsubstituted, branched or unbranched acyl; substituted or unsubstituted, branched or unbranched aryl; substituted or unsubstituted, branched or unbranched heteroaryl; —OR A ; —C(═O)R A ; —CO 2 R A ; —CN; —SCN; —SR A ; —SOR A ; —SO 2 R A ; —NO 2 ; —N(R A ) 2 ; —NHR A ; —NHC(O)R A ; or —C(R A ) 3 ; wherein each occurrence of R A is independently a hydrogen, a protecting group, an aliphatic moiety, a heteroaliphatic moiety, an acyl moiety; an aryl moiety; a heteroaryl moiety; alkoxy; aryloxy; alkylthio; arylthio; amino, alkylamino, dialkylamino, heteroaryloxy; or heteroarylthio moiety. In certain embodiments, L is
In certain embodiments, L is
In certain embodiments, L is an unbranched, unsubstituted, acyclic alkyl chain. In certain embodiments, L is
In other embodiments, L is
In certain other embodiments, L is
In other embodiments, L is
In yet other embodiments, L is
In certain embodiments, L is a substituted, acyclic aliphatic chain. In certain embodiments, L is
In certain embodiments, L is an unbranched, unsubstituted, acyclic heteroaliphatic chain. In certain particular embodiments, L is
wherein n is an integer between 0 and 10, inclusive; preferably, between 0 and 5, inclusive; and m is an integer between 0 and 10, inclusive; preferably, between 0 and 5, inclusive. In certain particular embodiments, L is
wherein n is an integer between 0 and 10, inclusive; preferably, between 0 and 5, inclusive; and m is an integer between 0 and 10, inclusive; preferably, between 0 and 5, inclusive. In certain particular embodiments, L is
wherein n is an integer between 0 and 10, inclusive; preferably, between 0 and 5, inclusive; m is an integer between 0 and 10, inclusive; preferably, between 0 and 5, inclusive; and R′ is hydrogen, C 1 -C 6 aliphatic, heteroaliphatic, aryl, heteroaryl, or acyl. In certain particular embodiments, L is
wherein n is an integer between 0 and 10, inclusive; preferably, between 0 and 5, inclusive; and m is an integer between 0 and 10, inclusive; preferably, between 0 and 5, inclusive.
In certain embodiments of the invention, compounds of formula (I) have the following structure as shown in formula (Ia):
wherein
n is an integer between 0 and 15, inclusive; preferably, between 0 and 10, inclusive; more preferably, between 1 and 8, inclusive; even more preferably, 4, 5, 6, 7, or 8; and
Ar is defined as above. In certain embodiments, n is 5. In other embodiments, n is 6. In still other embodiments, n is 7.
In certain embodiments of the invention, compounds of formula (I) have the following structure as shown in formula (Ib):
wherein
n is an integer between 0 and 15, inclusive; preferably, between 0 and 10, inclusive; more preferably, between 1 and 8, inclusive; even more preferably, 4, 5, 6, 7, or 8;
m is an integer between 1 and 5, inclusive; preferably, m is 1, 2, or 3; and
R 1 is hydrogen; halogen; cyclic or acyclic, substituted or unsubstituted, branched or unbranched aliphatic; cyclic or acyclic, substituted or unsubstituted, branched or unbranched heteroaliphatic; substituted or unsubstituted, branched or unbranched acyl; substituted or unsubstituted, branched or unbranched aryl; substituted or unsubstituted, branched or unbranched heteroaryl; —OR A ; —C(═O)R A ; —CO 2 R A ; —CN; —SCN; —SR A ; —SOR A ; —SO 2 R A ; —NO 2 ; —N(R A ) 2 ; —NHC(O)R A ; or —C(R A ) 3 ; wherein each occurrence of R A is independently a hydrogen, a protecting group, an aliphatic moiety, a heteroaliphatic moiety, an acyl moiety; an aryl moiety; a heteroaryl moiety; alkoxy; aryloxy; alkylthio; arylthio; amino, alkylamino, dialkylamino, heteroaryloxy; or heteroarylthio moiety. In certain embodiments, R 1 is hydrogen, halogen, hydroxy, amino, alkylamino, dialkylamino, nitroso, acyl, or C 1 -C 6 alkyl. In certain embodiments, R 1 is aryl. In certain embodiments, R 1 is a multicyclic aryl moiety. In other embodiments, R 1 is heteroaryl. In certain embodiments, R 1 is carbocyclic. In other embodiments, R 1 is heterocyclic. In certain embodiments R 1 comprises a 1,3-dioxane ring optionally substituted. In certain embodiments, n is 5. In other embodiments, n is 6. In still other embodiments, n is 7. In certain embodiments, m is 0. In other embodiments, m is 1. In still other embodiments, m is 2.
In certain embodiments of the invention, compounds of formula (I) are of the formula (Ic):
wherein
n is an integer between 0 and 15, inclusive; preferably, between 0 and 10, inclusive; more preferably, between 1 and 8, inclusive; even more preferably, 4, 5, 6, 7, or 8; and
R 1 is hydrogen; halogen; cyclic or acyclic, substituted or unsubstituted, branched or unbranched aliphatic; cyclic or acyclic, substituted or unsubstituted, branched or unbranched heteroaliphatic; substituted or unsubstituted, branched or unbranched acyl; substituted or unsubstituted, branched or unbranched aryl; substituted or unsubstituted, branched or unbranched heteroaryl; —OR A ; —C(═O)R A ; —CO 2 R A ; —CN; —SCN; —SR A ; —SOR A ; —SO 2 R A ; —NO 2 ; —N(R A ) 2 ; —NHC(O)R A ; or —C(R A ) 3 ; wherein each occurrence of R A is independently a hydrogen, a protecting group, an aliphatic moiety, a heteroaliphatic moiety, an acyl moiety; an aryl moiety; a heteroaryl moiety; alkoxy; aryloxy; alkylthio; arylthio; amino, alkylamino, dialkylamino, heteroaryloxy; or heteroarylthio moiety. In certain embodiments, R 1 is hydrogen, halogen, hydroxy, amino, alkylamino, dialkylamino, nitroso, acyl, or C 1 -C 6 alkyl. In certain embodiments, R 1 is aryl. In other embodiments, R 1 is heteroaryl. In certain embodiments, R 1 is carbocyclic. In other embodiments, R 1 is heterocyclic. In certain embodiments, n is 5. In other embodiments, n is 6. In still other embodiments, n is 7.
In certain embodiments of the invention, compounds of formula (I) are of the formula (Id):
wherein
n is an integer between 1 and 5, inclusive; preferably, between 1 and 3; more preferably, 1 or 2; and
R 1 is hydrogen; halogen; cyclic or acyclic, substituted or unsubstituted, branched or unbranched aliphatic; cyclic or acyclic, substituted or unsubstituted, branched or unbranched heteroaliphatic; substituted or unsubstituted, branched or unbranched acyl; substituted or unsubstituted, branched or unbranched aryl; substituted or unsubstituted, branched or unbranched heteroaryl; —OR A ; —C(═O)R A ; —CO 2 R A ; —CN; —SCN; —SR A ; —SOR A ; —SO 2 R A ; —NO 2 ; —N(R A ) 2 ; —NHC(O)R A ; or —C(R A ) 3 ; wherein each occurrence of R A is independently a hydrogen, a protecting group, an aliphatic moiety, a heteroaliphatic moiety, an acyl moiety; an aryl moiety; a heteroaryl moiety; alkoxy; aryloxy; alkylthio; arylthio; amino, alkylamino, dialkylamino, heteroaryloxy; or heteroarylthio moiety. In certain embodiments, R 1 is hydrogen, halogen, hydroxy, amino, alkylamino, dialkylamino, nitroso, acyl, or C 1 -C 6 alkyl. In certain embodiments, R 1 is aryl. In other embodiments, R 1 is heteroaryl. In certain embodiments, R 1 is carbocyclic. In other embodiments, R 1 is heterocyclic. In certain embodiments, n is 1. In other embodiments, n is 2.
In certain embodiments of the invention, compounds of formula (I) are of the formula (Ie):
wherein R 1 is defined as above.
In certain embodiments of the invention, compounds of formula (I) have the following stereochemistry and structure as shown in formula (If):
wherein A, L and Ar are defined as above; and
n is an integer between 0 and 10, inclusive; preferably, between 0 and 5, inclusive; even more preferably, 0, 1, 2, or 3. In certain embodiments, Ar is phenyl.
In certain embodiments, compounds of formula (I) are of the formula (Ig):
wherein
A and L are defined as above;
R 2 is hydrogen; halogen; cyclic or acyclic, substituted or unsubstituted, branched or unbranched aliphatic; cyclic or acyclic, substituted or unsubstituted, branched or unbranched heteroaliphatic; substituted or unsubstituted, branched or unbranched acyl; substituted or unsubstituted, branched or unbranched aryl; substituted or unsubstituted, branched or unbranched heteroaryl; —OR B ; —C(═O)R B ; —CO 2 R B ; —CN; —SCN; —SR B ; —SOR B ; —SO 2 R B ; —NO 2 ; —N(R B ) 2 ; —NHC(O)R B ; or —C(R B ) 3 ; wherein each occurrence of R B is independently a hydrogen, a protecting group, an aliphatic moiety, a heteroaliphatic moiety, an acyl moiety; an aryl moiety; a heteroaryl moiety; alkoxy; aryloxy; alkylthio; arylthio; amino, alkylamino, dialkylamino, heteroaryloxy; or heteroarylthio moiety; and
R 3 is hydrogen; halogen; cyclic or acyclic, substituted or unsubstituted, branched or unbranched aliphatic; cyclic or acyclic, substituted or unsubstituted, branched or unbranched heteroaliphatic; substituted or unsubstituted, branched or unbranched acyl; substituted or unsubstituted, branched or unbranched aryl; substituted or unsubstituted, branched or unbranched heteroaryl; —OR C ; —C(═O)R C ; —CO 2 R C ; —CN; —SCN; —SR C ; —SORC; —SO 2 R C ; —NO 2 ; —N(R C ) 2 ; —NHC(O)R C ; or —C(R C ) 3 ; wherein each occurrence of R C is independently a hydrogen, a protecting group, an aliphatic moiety, a heteroaliphatic moiety, an acyl moiety; an aryl moiety; a heteroaryl moiety; alkoxy; aryloxy; alkylthio; arylthio; amino, alkylamino, dialkylamino, heteroaryloxy; or heteroarylthio moiety.
In certain embodiments, R 2 is hydrogen. In other embodiments, R 2 is hydroxyl or a protected hydroxyl group. In certain embodiments, R 2 is alkoxy. In yet other embodiments, R 2 is a lower alkyl, alkenyl, or alkynyl group. In certain embodiments, R 2 is —CH 2 —X(R B ) n , wherein X is O, S, N, or C, preferably O, S, or N; and n is 1, 2, or 3. In certain embodiments, R 2 is —CH 2 —OR B . In other embodiments, R 2 is —CH 2 —SR B . In yet other embodiments, R 2 is —CH 2 —R B . In other embodiments, R 2 is —CH 2 —N(R B ) 2 . In still other embodiments, R 2 is —CH 2 —NHR B . In certain embodiments of the invention, R B is one of:
wherein m and p are each independently integers from 0 to 3; q 1 is an integer from 1 to 6; R 2C is hydrogen, lower alkyl or a nitrogen protecting group; and each occurrence of R 2B is independently hydrogen, halogen, —CN, or WR W1 wherein W is O, S, NR W2 , —C(═O), —S(═O), —SO 2 , —C(═O)O—, —OC(═O), —C(═O)NR W2 , —NR W2 C(═O); wherein each occurrence of R W1 and R W2 is independently hydrogen, a protecting group, a prodrug moiety or an alkyl, cycloalkyl, heteroalkyl, heterocyclic, aryl or heteroaryl moiety, or, when W is NR W2 , R W1 and R W2 , taken together with the nitrogen atom to which they are attached, form a heterocyclic or heteroaryl moiety; or any two adjacent occurrences of R 2B , taken together with the atoms to which they are attached, form a substituted or unsubstituted, saturated or unsaturated alicyclic or heterocyclic moiety, or a substituted or unsubstituted aryl or heteroaryl moiety. In certain embodiments of the invention, R B is one of the structures:
wherein m is an integer from 1 to 4; R 2C is hydrogen, lower alkyl or a nitrogen protecting group; and each occurrence of R 2B is independently hydrogen, halogen, —CN, or WR W1 wherein W is O, S, NR W2 , —C(═O), —S(═O), —SO 2 , —C(═O)O—, —OC(═O), —(═O)NR W2 , —NR W2 C(═O); wherein each occurrence of R W1 and R W2 is independently hydrogen, a protecting group, a prodrug moiety or an alkyl, cycloalkyl, heteroalkyl, heterocyclic, aryl or heteroaryl moiety, or, when W is NR W2 , R W1 and R W2 , taken together with the nitrogen atom to which they are attached, form a heterocyclic or heteroaryl moiety; or any two adjacent occurrences of R 2B , taken together with the atoms to which they are attached, form a substituted or unsubstituted, saturated or unsaturated alicyclic or heterocyclic moiety, or a substituted or unsubstituted aryl or heteroaryl moiety.
In certain embodiments, —X(R B ) n has one of the structures:
In certain embodiments, R 2 is
wherein X is N and Y is NH, S, or O. In other embodiments, R 2 is
In certain embodiments, R 3 is substituted or unsubstituted aryl. In certain embodiments, R 3 is substituted or unsubstituted phenyl. In certain particular embodiments, R 3 is monosubstituted phenyl. In certain embodiments, R 3 is para-substituted phenyl. In certain embodiments, R 3 is
wherein R 3 ′ is hydrogen, a protecting group, a solid support unit, an alkyl, acyl, cycloalkyl, heteroalkyl, heterocyclic, aryl, heteroaryl, -(alkyl)aryl, -(alkyl)heteroaryl, -(heteroalkyl)aryl, or -(heteroalkyl)heteroaryl moiety. In certain embodiments, R 3 is
In other embodiments, R 3 is substituted or unsubstituted heteroaryl.
In certain embodiments, the stereochemistry of formula (Ig) is defined as follows:
In certain embodiments of the invention, compounds of formula (I) are of the formula (Ih):
wherein
A and L are defined as above;
n is an integer between 0 and 10, inclusive; preferably, between 1 and 6, inclusive; more preferably, between 1 and 3, inclusive; and even more preferably, 0, 1, 2, or 3;
R 2 is hydrogen; halogen; cyclic or acyclic, substituted or unsubstituted, branched or unbranched aliphatic; cyclic or acyclic, substituted or unsubstituted, branched or unbranched heteroaliphatic; substituted or unsubstituted, branched or unbranched acyl; substituted or unsubstituted, branched or unbranched aryl; substituted or unsubstituted, branched or unbranched heteroaryl; —OR B ; —C(═O)R B ; —CO 2 R B ; —CN; —SCN; —SR B ; —SOR B ; —SO 2 R B ; —NO 2 ; —N(R B ) 2 ; —NHC(O)R B ; or —C(R B ) 3 ; wherein each occurrence of R B is independently a hydrogen, a protecting group, an aliphatic moiety, a heteroaliphatic moiety, an acyl moiety; an aryl moiety; a heteroaryl moiety; alkoxy; aryloxy; alkylthio; arylthio; amino, alkylamino, dialkylamino, heteroaryloxy; or heteroarylthio moiety; and
R 3 is hydrogen; halogen; cyclic or acyclic, substituted or unsubstituted, branched or unbranched aliphatic; cyclic or acyclic, substituted or unsubstituted, branched or unbranched heteroaliphatic; substituted or unsubstituted, branched or unbranched acyl; substituted or unsubstituted, branched or unbranched aryl; substituted or unsubstituted, branched or unbranched heteroaryl; —OR C ; —C(═O)R C ; —CO 2 R C ; —CN; —SCN; —SR C ; —SOR C ; —SO 2 R C ; —NO 2 ; —N(R C ) 2 ; —NHC(O)R C ; or —C(R C ) 3 ; wherein each occurrence of R C is independently a hydrogen, a protecting group, an aliphatic moiety, a heteroaliphatic moiety, an acyl moiety; an aryl moiety; a heteroaryl moiety; alkoxy; aryloxy; alkylthio; arylthio; amino, alkylamino, dialkylamino, heteroaryloxy; or heteroarylthio moiety.
In certain embodiments, R 2 is hydrogen. In other embodiments, R 2 is hydroxyl or a protected hydroxyl group. In certain embodiments, R 2 is alkoxy. In yet other embodiments, R 2 is a lower alkyl, alkenyl, or alkynyl group. In certain embodiments, R 2 is —CH 2 —X(R B ) n , wherein X is O, S, N, or C, preferably O, S, or N; and n is 1, 2, or 3. In certain embodiments, R 2 is —CH 2 —OR B . In other embodiments, R 2 is CH 2 —SR B . In yet other embodiments, R 2 is —CH 2 —R B . In other embodiments, R 2 is —CH 2 —N(R B ) 2 . In still other embodiments, R 2 is —CH 2 —NHR B . In certain embodiments of the invention, R B is one of:
wherein m and p are each independently integers from 0 to 3; q 1 is an integer from 1 to 6; R 2C is hydrogen, lower alkyl or a nitrogen protecting group; and each occurrence of R 2B is independently hydrogen, halogen, —CN, or WR W1 wherein W is O, S, NR W2 , —C(═O), —S(═O), —SO 2 , —C(═O)O—, —OC(═O), —C(═O)NR W2 , —NR W2 C(═O); wherein each occurrence of R W1 and R W2 is independently hydrogen, a protecting group, a prodrug moiety or an alkyl, cycloalkyl, heteroalkyl, heterocyclic, aryl or heteroaryl moiety, or, when W is NR W2 , R W1 and R W2 , taken together with the nitrogen atom to which they are attached, form a heterocyclic or heteroaryl moiety; or any two adjacent occurrences of R 2B , taken together with the atoms to which they are attached, form a substituted or unsubstituted, saturated or unsaturated alicyclic or heterocyclic moiety, or a substituted or unsubstituted aryl or heteroaryl moiety. In certain embodiments of the invention, R B is one of the structures:
wherein m is an integer from 1 to 4; R 2C is hydrogen, lower alkyl or a nitrogen protecting group; and each occurrence of R 2B is independently hydrogen, halogen, —CN, or WR W1 wherein W is O, S, NR W2 , —C(═O), —S(═O), —SO 2 , —C(═O)O—, —OC(═O), —C(═O)NR W2 , —NR W2 C(═O); wherein each occurrence of R W1 and R W2 is independently hydrogen, a protecting group, a pro drug moiety or an alkyl, cycloalkyl, heteroalkyl, heterocyclic, aryl or heteroaryl moiety, or, when W is NR W2 , R W1 and R w2 , taken together with the nitrogen atom to which they are attached, form a heterocyclic or heteroaryl moiety; or any two adjacent occurrences of R 2B , taken together with the atoms to which they are attached, form a substituted or unsubstituted, saturated or unsaturated alicyclic or heterocyclic moiety, or a substituted or unsubstituted aryl or heteroaryl moiety.
In certain embodiments, —X(R B ) n has one of the structures:
In certain embodiments, R 2 is
wherein X is N and Y is NH, S, or O. In other embodiments, R 2 is
In certain embodiments, R 3 is substituted or unsubstituted aryl. In certain embodiments, R 3 is substituted or unsubstituted phenyl. In certain particular embodiments, R 3 is monosubstituted phenyl. In certain embodiments, R 3 is para-substituted phenyl. In certain embodiments, R 3 is
wherein R 3 ′ is hydrogen, a protecting group, a solid support unit, an alkyl, acyl, cycloalkyl, heteroalkyl, heterocyclic, aryl, heteroaryl, —(alkyl)aryl, -(alkyl)heteroaryl, -(heteroalkyl)aryl, or -(heteroalkyl)heteroaryl moiety. In certain embodiments, R 3 is
In other embodiments, R 3 is substituted or unsubstituted heteroaryl.
In certain embodiments, the stereochemistry of formula (Ih) is defined as follows:
In certain embodiments of the invention, compounds of formula (I) have structure as shown in formula (Ii):
wherein
A and L are defined as above;
R 2 is hydrogen; halogen; cyclic or acyclic, substituted or unsubstituted, branched or unbranched aliphatic; cyclic or acyclic, substituted or unsubstituted, branched or unbranched heteroaliphatic; substituted or unsubstituted, branched or unbranched acyl; substituted or unsubstituted, branched or unbranched aryl; substituted or unsubstituted, branched or unbranched heteroaryl; —OR B ; —C(═O)R B ; —CO 2 R B ; —CN; —SCN; —SR B ; —SOR B ; —SO 2 R B ; —NO 2 ; —N(R B ) 2 ; —NHC(O)R B ; or —C(R B ) 3 ; wherein each occurrence of R B is independently a hydrogen, a protecting group, an aliphatic moiety, a heteroaliphatic moiety, an acyl moiety; an aryl moiety; a heteroaryl moiety; alkoxy; aryloxy; alkylthio; arylthio; amino, alkylamino, dialkylamino, heteroaryloxy; or heteroarylthio moiety; and
R 3 is hydrogen; halogen; cyclic or acyclic, substituted or unsubstituted, branched or unbranched aliphatic; cyclic or acyclic, substituted or unsubstituted, branched or unbranched heteroaliphatic; substituted or unsubstituted, branched or unbranched acyl; substituted or unsubstituted, branched or unbranched aryl; substituted or unsubstituted, branched or unbranched heteroaryl; —OR C ; —C(═O)R C ; —CO 2 R C ; —CN; —SCN; —SR C ; —SOR C ; —SO 2 R C ; —NO 2 ; —N(R C ) 2 ; —NHC(O)R C ; or —C(R C ) 3 ; wherein each occurrence of R C is independently a hydrogen, a protecting group, an aliphatic moiety, a heteroaliphatic moiety, an acyl moiety; an aryl moiety; a heteroaryl moiety; alkoxy; aryloxy; alkylthio; arylthio; amino, alkylamino, dialkylamino, heteroaryloxy; or heteroarylthio moiety.
In certain embodiments, R 2 is hydrogen. In other embodiments, R 2 is hydroxyl or a protected hydroxyl group. In certain embodiments, R 2 is alkoxy. In yet other embodiments, R 2 is a lower alkyl, alkenyl, or alkynyl group. In certain embodiments, R 2 is —CH 2 —X(R B ) n , wherein X is O, S, N, or C, preferably O, S, or N; and n is 1, 2, or 3. In certain embodiments, R 2 is —CH 2 —OR B . In other embodiments, R 2 is —CH 2 —SR B . In yet other embodiments, R 2 is —CH 2 —R B . In other embodiments, R 2 is —CH 2 —N(R B ) 2 . In still other embodiments, R 2 is —CH 2 —NHR B . In certain embodiments of the invention, R B is one of:
wherein m and p are each independently integers from 0 to 3; q 1 is an integer from 1 to 6; R 2C is hydrogen, lower alkyl or a nitrogen protecting group; and each occurrence of R 2B is independently hydrogen, halogen, —CN, or WR W1 wherein W is O, S, NR W2 , —C(═O), —S(═O), —SO 2 , —C(═O)O—, —OC(═O), —C(═O)NR NR W2 C(═O); wherein each occurrence of R W1 and R W2 is independently hydrogen, a protecting group, a prodrug moiety or an alkyl, cycloalkyl, heteroalkyl, heterocyclic, aryl or heteroaryl moiety, or, when W is NR W2 , R W1 and R W2 , taken together with the nitrogen atom to which they are attached, form a heterocyclic or heteroaryl moiety; or any two adjacent occurrences of R 2B , taken together with the atoms to which they are attached, form a substituted or unsubstituted, saturated or unsaturated alicyclic or heterocyclic moiety, or a substituted or unsubstituted aryl or heteroaryl moiety. In certain embodiments of the invention, R B is one of the structures:
wherein m is an integer from 1 to 4; R 2C is hydrogen, lower alkyl or a nitrogen protecting group; and each occurrence of R 2B is independently hydrogen, halogen, —CN, or WR W1 wherein W is O, S, NR W2 , —C(═O), —S(═O), —SO 2 , —C(═O)O—, —OC(═O), —C(═O)NR W2 , —NR W2 C(═O); wherein each occurrence of R W1 and R W2 is independently hydrogen, a protecting group, a prodrug moiety or an alkyl, cycloalkyl, heteroalkyl, heterocyclic, aryl or heteroaryl moiety, or, when W is NR W2 , R W1 and R W2 , taken together with the nitrogen atom to which they are attached, form a heterocyclic or heteroaryl moiety; or any two adjacent occurrences of R 2B , taken together with the atoms to which they are attached, form a substituted or unsubstituted, saturated or unsaturated alicyclic or heterocyclic moiety, or a substituted or unsubstituted aryl or heteroaryl moiety.
In certain embodiments, —X(R B ) n has one of the structures:
In certain embodiments, R 2 is
wherein X is N and Y is NH, S, or O. In other embodiments, R 2 is
In certain embodiments, R 3 is substituted or unsubstituted aryl. In certain embodiments, R 3 is substituted or unsubstituted phenyl. In certain particular embodiments, R 3 is monosubstituted phenyl. In certain embodiments, R 3 is para-substituted phenyl. In certain embodiments, R 3 is
wherein R 3 ′ is hydrogen, a protecting group, a solid support unit, an alkyl, acyl, cycloalkyl, heteroalkyl, heterocyclic, aryl, heteroaryl, —(alkyl)aryl, -(alkyl)heteroaryl, -(heteroalkyl)aryl, or -(heteroalkyl)heteroaryl moiety. In certain embodiments, R 3 is
In other embodiments, R 3 is substituted or unsubstituted heteroaryl.
In certain embodiments, the stereochemistry of formula (Ii) is defined as follows:
In certain embodiments of the invention, compounds of formula (I) have the following stereochemistry and structure as shown in formula (Ij):
wherein
R 2 is hydrogen; halogen; cyclic or acyclic, substituted or unsubstituted, branched or unbranched aliphatic; cyclic or acyclic, substituted or unsubstituted, branched or unbranched heteroaliphatic; substituted or unsubstituted, branched or unbranched acyl; substituted or unsubstituted, branched or unbranched aryl; substituted or unsubstituted, branched or unbranched heteroaryl; —OR B ; —C(═O)R B ; —CO 2 R B ; —CN; —SCN; —SR B ; —SOR B ; —SO 2 R B ; —NO 2 ; —N(R B ) 2 ; —NHC(O)R B ; or —C(R B ) 3 ; wherein each occurrence of R B is independently a hydrogen, a protecting group, an aliphatic moiety, a heteroaliphatic moiety, an acyl moiety; an aryl moiety; a heteroaryl moiety; alkoxy; aryloxy; alkylthio; arylthio; amino, alkylamino, dialkylamino, heteroaryloxy; or heteroarylthio moiety; and
R 3 is hydrogen; halogen; cyclic or acyclic, substituted or unsubstituted, branched or unbranched aliphatic; cyclic or acyclic, substituted or unsubstituted, branched or unbranched heteroaliphatic; substituted or unsubstituted, branched or unbranched acyl; substituted or unsubstituted, branched or unbranched aryl; substituted or unsubstituted, branched or unbranched heteroaryl; —OR C ; —C(═O)R C ; —CO 2 R C ; —CN; —SCN; —SR C ; —SOR C ; —SO 2 R C ; —NO 2 ; —N(R C ) 2 ; —NHC(O)R C ; or —C(R C ) 3 ; wherein each occurrence of R C is independently a hydrogen, a protecting group, an aliphatic moiety, a heteroaliphatic moiety, an acyl moiety; an aryl moiety; a heteroaryl moiety; alkoxy; aryloxy; alkylthio; arylthio; amino, alkylamino, dialkylamino, heteroaryloxy; or heteroarylthio moiety.
In certain embodiments, R 2 is hydrogen. In other embodiments, R 2 is hydroxyl or a protected hydroxyl group. In certain embodiments, R 2 is alkoxy. In yet other embodiments, R 2 is a lower alkyl, alkenyl, or alkynyl group. In certain embodiments, R 2 is —CH 2 —X(R B ) n , wherein X is O, S, N, or C, preferably O, S, or N; and n is 1, 2, or 3. In certain embodiments, R 2 is —CH 2 —OR B . In other embodiments, R 2 is —CH 2 —SR B . In yet other embodiments, R 2 is —CH 2 —R B . In other embodiments, R 2 is —CH 2 —N(R B ) 2 . In still other embodiments, R 2 is —CH 2 —NHR B . In certain embodiments of the invention, R B is one of:
wherein m and p are each independently integers from 0 to 3; q 1 is an integer from 1 to 6; R 2C is hydrogen, lower alkyl or a nitrogen protecting group; and each occurrence of R 2B is independently hydrogen, halogen, —CN, or WR W1 wherein W is O, S, NR W2 , —C(═O), —S(═O), —SO 2 , —C(═O)O—, —OC(═O), —C(═O)NR W2 , —NR W2 C(═O); wherein each occurrence of R W1 and R W2 is independently hydrogen, a protecting group, a prodrug moiety or an alkyl, cycloalkyl, heteroalkyl, heterocyclic, aryl or heteroaryl moiety, or, when W is NR W2 , R W1 and R W2 , taken together with the nitrogen atom to which they are attached, form a heterocyclic or heteroaryl moiety; or any two adjacent occurrences of R 2B , taken together with the atoms to which they are attached, form a substituted or unsubstituted, saturated or unsaturated alicyclic or heterocyclic moiety, or a substituted or unsubstituted aryl or heteroaryl moiety. In certain embodiments of the invention, R B is one of the structures:
wherein m is an integer from 1 to 4; R 2C is hydrogen, lower alkyl or a nitrogen protecting group; and each occurrence of R 2B is independently hydrogen, halogen, —CN, or WR W1 wherein W is O, S, NR W2 , —C(═O), —S(═O), —SO 2 , —C(═O)O—, —OC(═O), —C(═O)NR W2 , —NR W2 C(═O); wherein each occurrence of R W1 and R W2 is independently hydrogen, a protecting group, a prodrug moiety or an alkyl, cycloalkyl, heteroalkyl, heterocyclic, aryl or heteroaryl moiety, or, when W is NR W2 , R W1 and R W2 , taken together with the nitrogen atom to which they are attached, form a heterocyclic or heteroaryl moiety; or any two adjacent occurrences of R 2B , taken together with the atoms to which they are attached, form a substituted or unsubstituted, saturated or unsaturated alicyclic or heterocyclic moiety, or a substituted or unsubstituted aryl or heteroaryl moiety.
In certain embodiments, —X(R B ) n has one of the structures:
In certain embodiments, R 2 is
wherein X is N and Y is NH, S, or O. In other embodiments, R 2 is
In certain embodiments, R 3 is substituted or unsubstituted aryl. In certain embodiments, R 3 is substituted or unsubstituted phenyl. In certain particular embodiments, R 3 is monosubstituted phenyl. In certain embodiments, R 3 is para-substituted phenyl. In certain embodiments, R 3 is
wherein R 3 ′ is hydrogen, a protecting group, a solid support unit, an alkyl, acyl, cycloalkyl, heteroalkyl, heterocyclic, aryl, heteroaryl, —(alkyl)aryl, -(alkyl)heteroaryl, -(heteroalkyl)aryl, or -heteroalkyl)heteroaryl moiety. In certain embodiments, R 3 is
In other embodiments, R 3 is substituted or unsubstituted heteroaryl.
Another class of compounds of special interest includes those compounds of the invention as described above and in certain subclasses herein, wherein R 3 is a substituted phenyl moiety and the compounds have the formula (Il):
wherein
L, A, X, and R B are defined as above;
n is an integer between 0 and 5, inclusive; preferably, between, 1 and 3; more preferably, 2; and
Z is hydrogen, —(CH 2 ) q OR Z , —(CH 2 ) q SR Z , —(CH 2 ) q N(R Z ) 2 , —C(═O)R Z , —C(═O)N(R Z ) 2 , or an alkyl, heteroalkyl, aryl, heteroaryl, -(alkyl)aryl, -(alkyl)heteroaryl, -(heteroalkyl)aryl, or -(heteroalkyl)heteroaryl moiety, wherein q is 0-4, and wherein each occurrence of R Z is independently hydrogen, a protecting group, a solid support unit, or an alkyl, acyl, cycloalkyl, heteroalkyl, heterocyclic, aryl, heteroaryl, -(alkyl)aryl, -(alkyl)heteroaryl, -(heteroalkyl)aryl, or -(heteroalkyl)heteroaryl moiety. In certain embodiments, R Z is hydrogen. In other embodiments, R Z is C 1 -C 6 alkyl. In certain embodiments, R Z is an oxygen-protecting group.
Another class of compounds includes those compounds of formula (Il), wherein Z is —CH 2 OR Z , and the compounds have the general structure (Im):
wherein
R B , R Z , X, L, n, and A are defined generally above and in classes and subclasses herein. In certain embodiments, X is S. In other embodiments, X is O.
Yet another class of compounds of particular interest includes those compounds of formula (Ii), wherein X is S and the compounds have the general structure (In):
wherein
R B , X, L, n, and A are defined as above; and
R Z is as defined generally above and in classes and subclasses herein. Yet another class of compounds of special interest includes those compounds of formula (Il), wherein X is —NR 2A and the compounds have the general structure (Io):
wherein
R B , R Z , X, L, n, and A are defined generally above and in classes and subclasses herein.
Yet another class of compounds of special interest includes those compounds of formula (Ii), wherein X is O and the compounds have the general structure (Ip):
wherein
R B , R Z , X, L, n, and A are defined generally above and in classes and subclasses herein.
Exemplary compounds of the invention are shown:
Some of the foregoing compounds can comprise one or more asymmetric centers, and thus can exist in various isomeric forms, e.g., stereoisomers and/or diastereomers. Thus, inventive compounds and pharmaceutical compositions thereof may be in the form of an individual enantiomer, diastereomer or geometric isomer, or may be in the form of a mixture of stereoisomers. In certain embodiments, the compounds of the invention are enantiopure compounds. In certain other embodiments, mixtures of stereoisomers or diastereomers are provided.
Furthermore, certain compounds, as described herein may have one or more double bonds that can exist as either the Z or E isomer, unless otherwise indicated. The invention additionally encompasses the compounds as individual isomers substantially free of other isomers and alternatively, as mixtures of various isomers, e.g., racemic mixtures of stereoisomers. In addition to the above-mentioned compounds per se, this invention also encompasses pharmaceutically acceptable derivatives of these compounds and compositions comprising one or more compounds of the invention and one or more pharmaceutically acceptable excipients or additives.
Compounds of the invention may be prepared by crystallization of the compound under different conditions and may exist as one or a combination of polymorphs of the compound forming part of this invention. For example, different polymorphs may be identified and/or prepared using different solvents, or different mixtures of solvents for recrystallization; by performing crystallizations at different temperatures; or by using various modes of cooling, ranging from very fast to very slow cooling during crystallizations. Polymorphs may also be obtained by heating or melting the compound followed by gradual or fast cooling. The presence of polymorphs may be determined by solid probe NMR spectroscopy, IR spectroscopy, differential scanning calorimetry, powder X-ray diffractogram and/or other techniques. Thus, the present invention encompasses inventive compounds, their derivatives, their tautomeric forms, their stereoisomers, their polymorphs, their pharmaceutically acceptable salts their pharmaceutically acceptable solvates and pharmaceutically acceptable compositions containing them.
Synthetic Overview
The synthesis of the various monomeric compounds used to prepare the dimeric, multimeric, and polymeric compounds of the invention are known in the art. These published syntheses may be utilized to prepare the compounds of the invention. Exemplary synthetic methods for preparing compounds of the invention are described in U.S. Pat. Nos. 6,960,685; 6,897,220; 6,541,661; 6,512,123; 6,495,719; US 2006/0020131; US 2004/087631; US 2004/127522; US 2004/0072849; US 2003/0187027; WO 2005/018578; WO 2005/007091; WO 2005/007091; WO 2005/018578; WO 2004/046104; WO 2002/89782; each of which is incorporated herein by reference. In many cases, an amide moiety is changed to an ester moiety to prepare the inventive compounds.
An exemplary synthetic scheme for preparing SAHP is show in in FIG. 13 . Those of skill in the art will realize that based on this teaching and those in the art as referenced above one could prepare any of the esterase-sensitive compounds of the invention.
In yet another aspect of the invention, methods for producing intermediates useful for the preparation of certain compounds of the invention are provided.
In one aspect of the invention, a method for the synthesis of the core structure of certain compounds is provided, one method comprising steps of:
providing an epoxy alcohol having the structure:
reacting the epoxy alcohol with a reagent having the structure R 2 XH under suitable conditions to generate a diol having the core structure:
reacting the diol with a reagent having the structure R 3 CH(OMe) 2 under suitable conditions to generate a scaffold having the core structure:
wherein R 1 is hydrogen, or an aliphatic, alicyclic, heteroaliphatic, heterocyclic, aromatic or heteroaromatic moiety;
R 2 is hydrogen, a protecting group, or an aliphatic, alicyclic, heteroaliphatic, heterocyclic, aromatic or heteroaromatic moiety;
X is —O—, —C(R 2A ) 2 —, —S—, or —NR 2A , wherein R 2A is hydrogen, a protecting group, or an aliphatic, alicyclic, heteroaliphatic, heterocyclic, aromatic or heteroaromatic moiety;
or wherein two or more occurrences of R 2 and R 2A , taken together, form an alicyclic or heterocyclic moiety, or an aryl or heteroaryl moiety;
R 3 is an aliphatic, alicyclic, heteroaliphatic, heterocyclic, aromatic or heteroaromatic moiety; and
R Z is an aliphatic, alicyclic, heteroaliphatic, heterocyclic, aromatic or heteroaromatic moiety and is optionally attached to a solid support.
In certain exemplary embodiments, the epoxy alcohol has the structure:
the diol has the structure:
and the core scaffold has the structure:
In certain other exemplary embodiments, the epoxy alcohol has the structure:
the diol has the structure:
and the core scaffold has the structure:
In certain embodiments, R 3 has the following structure:
and the method described above generates the structure:
In another aspect of the invention, a method for the synthesis of the core structure of certain compounds of the invention is provided, one method comprising steps of:
providing an epoxy alcohol having the structure:
reacting the epoxy alcohol with a reagent having the structure R 2 XH under suitable conditions to generate a diol having the core structure:
subjecting the diol to a reagent having the structure:
wherein R 4C is a nitrogen protecting group; to suitable conditions to generate an amine having the structure:
reacting the amine with a reagent having the structure:
under suitable conditions to generate a scaffold having the core structure:
wherein R 1 is hydrogen, or an aliphatic, alicyclic, heteroaliphatic, heterocyclic, aromatic or heteroaromatic moiety;
R 2 is hydrogen, a protecting group, or an aliphatic, alicyclic, heteroaliphatic, heterocyclic, aromatic or heteroaromatic moiety;
X is —O—, —C(R 2A ) 2 —, —S—, or —NR 2A —, wherein R 2A is hydrogen, a protecting group, or an aliphatic, alicyclic, heteroaliphatic, heterocyclic, aromatic or heteroaromatic moiety;
or wherein two or more occurrences of R 2 and R 2A , taken together, form an alicyclic or heterocyclic moiety, or an aryl or heteroaryl moiety;
r is 0 or 1;
s is an integer from 2-5;
w is an integer from 0-4;
R 4A comprises a metal chelator;
each occurrence of R 4D is independently hydrogen, alkyl, heteroalkyl, cycloalkyl, heterocyclic, alkenyl, alkynyl, aryl, heteroaryl, halogen, CN, NO 2 , or WR W1 wherein W is O, S, NR W2 , —C(═O), —S(═O), —SO 2 , —C(═O)O—, —OC(═O), —C(═O)NR W2 , —NR W2 C(═O); wherein each occurrence of R W1 and R W2 is independently hydrogen, a protecting group, a prodrug moiety or an alkyl, cycloalkyl, heteroalkyl, heterocyclic, aryl or heteroaryl moiety, or, when W is NR W2 , R W1 and R W2 , taken together with the nitrogen atom to which they are attached, form a heterocyclic or heteroaryl moiety; or any two adjacent occurrences of R 2B , taken together with the atoms to which they are attached, form a substituted or unsubstituted, saturated or unsaturated alicyclic or heterocyclic moiety, or a substituted or unsubstituted aryl or heteroaryl moiety; and
R Z is an aliphatic, alicyclic, heteroaliphatic, heterocyclic, aromatic or heteroaromatic moiety and is optionally attached to a solid support.
In certain exemplary embodiments, the epoxy alcohol has the structure:
the diol has the structure:
the amine has the structure:
and the core scaffold has the structure:
In certain exemplary embodiments, the epoxy alcohol has the structure:
the diol has the structure:
the amine has the structure:
and the core scaffold has the structure:
In certain embodiments, the methods described above are carried out in solution phase. In certain other embodiments, the methods described above are carried out on a solid phase. In certain embodiments, the synthetic method is amenable to high-throughput techniques or to techniques commonly used in combinatorial chemistry.
Pharmaceutical Compositions
As discussed above, the present invention provides novel compounds having antitumor and antiproliferative activity, and thus the inventive compounds are useful for the treatment of cancer (e.g., cutaneous T-cell lymphoma). Benign proliferative diseases may also be treated using the inventive compounds. The compounds are also useful in the treatment of other diseases or condition that benefit from inhibition of deacetylation activity (e.g. HDAC inhibition). In certain embodiments, the compounds are useful in the treatment of baldness based on the discovery that HDAC inhibition (particularly, HDAC6 inhibition) blocks androgen signaling vis hsp90. HDAC inhibition has also been shown to inhibit estrogen signaling. In certain embodiments, the compounds are useful in blocking the hyperpigmentation of skin by HDAC inhibition.
Accordingly, in another aspect of the present invention, pharmaceutical compositions are provided, which comprise any one of the compounds described herein (or a prodrug, pharmaceutically acceptable salt or other pharmaceutically acceptable derivative thereof), and optionally comprise a pharmaceutically acceptable carrier. In certain embodiments, these compositions optionally further comprise one or more additional therapeutic agents. Alternatively, a compound of this invention may be administered to a patient in need thereof in combination with the administration of one or more other therapeutic agents. For example, additional therapeutic agents for conjoint administration or inclusion in a pharmaceutical composition with a compound of this invention may be an approved chemotherapeutic agent, or it may be any one of a number of agents undergoing approval in the Food and Drug Administration that ultimately obtain approval for the treatment of hair loss, skin hyperpigmentation, protozoal infections, and/or any disorder associated with cellular hyperproliferation. In certain other embodiments, the additional therapeutic agent is an anticancer agent, as discussed in more detail herein. In certain other embodiments, the compositions of the invention are useful for the treatment of protozoal infections.
It will also be appreciated that certain of the compounds of present invention can exist in free form for treatment, or where appropriate, as a pharmaceutically acceptable derivative thereof. According to the present invention, a pharmaceutically acceptable derivative includes, but is not limited to, pharmaceutically acceptable salts, esters, salts of such esters, or a pro-drug or other adduct or derivative of a compound of this invention which upon administration to a patient in need is capable of providing, directly or indirectly, a compound as otherwise described herein, or a metabolite or residue thereof.
As used herein, the term “pharmaceutically acceptable salt” refers to those salts which are, within the scope of sound medical judgment, suitable for use in contact with the tissues of humans and lower animals without undue toxicity, irritation, allergic response and the like, and are commensurate with a reasonable benefit/risk ratio. Pharmaceutically acceptable salts of amines, carboxylic acids, and other types of compounds, are well known in the art. For example, S. M. Berge, et al. describe pharmaceutically acceptable salts in detail in J Pharmaceutical Sciences, 66:1-19 (1977), incorporated herein by reference. The salts can be prepared in situ during the final isolation and purification of the compounds of the invention, or separately by reacting a free base or free acid function with a suitable reagent, as described generally below. For example, a free base function can be reacted with a suitable acid. Furthermore, where the compounds of the invention carry an acidic moiety, suitable pharmaceutically acceptable salts thereof may, include metal salts such as alkali metal salts, e.g. sodium or potassium salts; and alkaline earth metal salts, e.g. calcium or magnesium salts. Examples of pharmaceutically acceptable, nontoxic acid addition salts are salts of an amino group formed with inorganic acids such as hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid and perchloric acid or with organic acids such as acetic acid, oxalic acid, maleic acid, tartaric acid, citric acid, succinic acid or malonic acid or by using other methods used in the art such as ion exchange. Other pharmaceutically acceptable salts include adipate, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bisulfate, borate, butyrate, camphorate, camphorsulfonate, citrate, cyclopentanepropionate, digluconate, dodecylsulfate, ethanesulfonate, formate, fumarate, glucoheptonate, glycerophosphate, gluconate, hemisulfate, heptanoate, hexanoate, hydroiodide, 2-hydroxy-ethanesulfonate, lactobionate, lactate, laurate, lauryl sulfate, malate, maleate, malonate, methanesulfonate, 2-naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmitate, pamoate, pectinate, persulfate, 3-phenylpropionate, phosphate, picrate, pivalate, propionate, stearate, succinate, sulfate, tartrate, thiocyanate, p-toluenesulfonate, undecanoate, valerate salts, and the like. Representative alkali or alkaline earth metal salts include sodium, lithium, potassium, calcium, magnesium, and the like. Further pharmaceutically acceptable salts include, when appropriate, nontoxic ammonium, quaternary ammonium, and amine cations formed using counterions such as halide, hydroxide, carboxylate, sulfate, phosphate, nitrate, loweralkyl sulfonate and aryl sulfonate.
Additionally, as used herein, the term “pharmaceutically acceptable ester” refers to esters that hydrolyze in vivo and include those that break down readily in the human body to leave the parent compound or a salt thereof. Suitable ester groups include, for example, those derived from pharmaceutically acceptable aliphatic carboxylic acids, particularly alkanoic, alkenoic, cycloalkanoic and alkanedioic acids, in which each alkyl or alkenyl moeity advantageously has not more than 6 carbon atoms. Examples of particular esters include formates, acetates, propionates, butyrates, acrylates and ethylsuccinates.
Furthermore, the term “pharmaceutically acceptable prodrugs” as used herein refers to those prodrugs of the compounds of the present invention which are, within the scope of sound medical judgment, suitable for use in contact with the issues of humans and lower animals with undue toxicity, irritation, allergic response, and the like, commensurate with a reasonable benefit/risk ratio, and effective for their intended use, as well as the zwitterionic forms, where possible, of the compounds of the invention. The term “prodrug” refers to compounds that are rapidly transformed in vivo to yield the parent compound of the above formula, for example by hydrolysis in blood. A thorough discussion is provided in T. Higuchi and V. Stella, Pro-drugs as Novel Delivery Systems, Vol. 14 of the A.C.S. Symposium Series, and in Edward B. Roche, ed., Bioreversible Carriers in Drug Design, American Pharmaceutical Association and Pergamon Press, 1987, both of which are incorporated herein by reference.
As described above, the pharmaceutical compositions of the present invention additionally comprise a pharmaceutically acceptable carrier, which, as used herein, includes any and all solvents, diluents, or other liquid vehicle, dispersion or suspension aids, surface active agents, isotonic agents, thickening or emulsifying agents, preservatives, solid binders, lubricants and the like, as suited to the particular dosage form desired. Remington's Pharmaceutical Sciences, Sixteenth Edition, E. W. Martin (Mack Publishing Co., Easton, Pa., 1980) discloses various carriers used in formulating pharmaceutical compositions and known techniques for the preparation thereof. Except insofar as any conventional carrier medium is incompatible with the compounds of the invention, such as by producing any undesirable biological effect or otherwise interacting in a deleterious manner with any other component(s) of the pharmaceutical composition, its use is contemplated to be within the scope of this invention. Some examples of materials which can serve as pharmaceutically acceptable carriers include, but are not limited to, sugars such as lactose, glucose and sucrose; starches such as corn starch and potato starch; cellulose and its derivatives such as sodium carboxymethyl cellulose, ethyl cellulose and cellulose acetate; powdered tragacanth; malt; gelatine; talc; excipients such as cocoa butter and suppository waxes; oils such as peanut oil, cottonseed oil; safflower oil, sesame oil; olive oil; corn oil and soybean oil; glycols; such as propylene glycol; esters such as ethyl oleate and ethyl laurate; agar; buffering agents such as magnesium hydroxide and aluminum hydroxide; alginic acid; pyrogenfree water; isotonic saline; Ringer's solution; ethyl alcohol, and phosphate buffer solutions, as well as other non-toxic compatible lubricants such as sodium lauryl sulfate and magnesium stearate, as well as coloring agents, releasing agents, coating agents, sweetening, flavoring and perfuming agents, preservatives and antioxidants can also be present in the composition, according to the judgment of the formulator.
Liquid dosage forms for oral administration include, but are not limited to, pharmaceutically acceptable emulsions, microemulsions, solutions, suspensions, syrups and elixirs. In addition to the active compounds, the liquid dosage forms may contain inert diluents commonly used in the art such as, for example, water or other solvents, solubilizing agents and emulsifiers such as ethyl alcohol, isopropyl alcohol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 1,3-butylene glycol, dimethylformamide, oils (in particular, cottonseed, groundnut, corn, germ, olive, castor, and sesame oils), glycerol, tetrahydrofurfuryl alcohol, polyethylene glycols and fatty acid esters of sorbitan, and mixtures thereof. Besides inert diluents, the oral compositions can also include adjuvants such as wetting agents, emulsifying and suspending agents, sweetening, flavoring, and perfuming agents.
Injectable preparations, for example, sterile injectable aqueous or oleaginous suspensions may be formulated according to the known art using suitable dispersing or wetting agents and suspending agents. The sterile injectable preparation may also be a sterile injectable solution, suspension or emulsion in a nontoxic parenterally acceptable diluent or solvent, for example, as a solution in 1,3-butanediol. Among the acceptable vehicles and solvents that may be employed are water, Ringer's solution, U.S.P. and isotonic sodium chloride solution. In addition, sterile, fixed oils are conventionally employed as a solvent or suspending medium. For this purpose any bland fixed oil can be employed including synthetic mono-or diglycerides. In addition, fatty acids such as oleic acid are used in the preparation of injectables.
The injectable formulations can be sterilized, for example, by filtration through a bacterial-retaining filter, or by incorporating sterilizing agents in the form of sterile solid compositions which can be dissolved or dispersed in sterile water or other sterile injectable medium prior to use.
In order to prolong the effect of a drug, it is often desirable to slow the absorption of the drug from subcutaneous or intramuscular injection. This may be accomplished by the use of a liquid suspension or crystalline or amorphous material with poor water solubility. The rate of absorption of the drug then depends upon its rate of dissolution that, in turn, may depend upon crystal size and crystalline form. Alternatively, delayed absorption of a parenterally administered drug form is accomplished by dissolving or suspending the drug in an oil vehicle. Injectable depot forms are made by forming microencapsule matrices of the drug in biodegradable polymers such as polylactide-polyglycolide. Depending upon the ratio of drug to polymer and the nature of the particular polymer employed, the rate of drug release can be controlled. Examples of other biodegradable polymers include (poly(orthoesters) and poly(anhydrides). Depot injectable formulations are also prepared by entrapping the drug in liposomes or microemulsions which are compatible with body tissues.
Compositions for rectal or vaginal administration are preferably suppositories which can be prepared by mixing the compounds of this invention with suitable non-irritating excipients or carriers such as cocoa butter, polyethylene glycol or a suppository wax which are solid at ambient temperature but liquid at body temperature and therefore melt in the rectum or vaginal cavity and release the active compound.
Solid dosage forms for oral administration include capsules, tablets, pills, powders, and granules. In such solid dosage forms, the active compound is mixed with at least one inert, pharmaceutically acceptable excipient or carrier such as sodium citrate or dicalcium phosphate and/or a) fillers or extenders such as starches, lactose, sucrose, glucose, mannitol, and silicic acid, b) binders such as, for example, carboxymethylcellulose, alginates, gelatin, polyvinylpyrrolidinone, sucrose, and acacia, c) humectants such as glycerol, d) disintegrating agents such as agar-agar, calcium carbonate, potato or tapioca starch, alginic acid, certain silicates, and sodium carbonate, e) solution retarding agents such as paraffin, f) absorption accelerators such as quaternary ammonium compounds, g) wetting agents such as, for example, cetyl alcohol and glycerol monostearate, h) absorbents such as kaolin and bentonite clay, and i) lubricants such as talc, calcium stearate, magnesium stearate, solid polyethylene glycols, sodium lauryl sulfate, and mixtures thereof. In the case of capsules, tablets and pills, the dosage form may also comprise buffering agents.
Solid compositions of a similar type may also be employed as fillers in soft and hard-filled gelatin capsules using such excipients as lactose or milk sugar as well as high molecular weight polyethylene glycols and the like. The solid dosage forms of tablets, dragees, capsules, pills, and granules can be prepared with coatings and shells such as enteric coatings and other coatings well known in the pharmaceutical formulating art. They may optionally contain opacifying agents and can also be of a composition that they release the active ingredient(s) only, or preferentially, in a certain part of the intestinal tract, optionally, in a delayed manner. Examples of embedding compositions that can be used include polymeric substances and waxes. Solid compositions of a similar type may also be employed as fillers in soft and hard-filled gelatin capsules using such excipients as lactose or milk sugar as well as high molecular weight polethylene glycols and the like.
The active compounds can also be in micro-encapsulated form with one or more excipients as noted above. The solid dosage forms of tablets, dragees, capsules, pills, and granules can be prepared with coatings and shells such as enteric coatings, release controlling coatings and other coatings well known in the pharmaceutical formulating art. In such solid dosage forms the active compound may be admixed with at least one inert diluent such as sucrose, lactose and starch. Such dosage forms may also comprise, as in normal practice, additional substances other than inert diluents, e.g., tableting lubricants and other tableting aids such as magnesium stearate and microcrystalline cellulose. In the case of capsules, tablets and pills, the dosage forms may also comprise buffering agents. They may optionally contain opacifying agents and can also be of a composition that they release the active ingredient(s) only, or preferentially, in a certain part of the intestinal tract, optionally, in a delayed manner. Examples of embedding compositions which can be used include polymeric substances and waxes.
The present invention encompasses pharmaceutically acceptable topical formulations of inventive compounds. The term “pharmaceutically acceptable topical formulation”, as used herein, means any formulation which is pharmaceutically acceptable for intradermal administration of a compound of the invention by application of the formulation to the epidermis. In certain embodiments of the invention, the topical formulation comprises a carrier system. Pharmaceutically effective carriers include, but are not limited to, solvents (e.g., alcohols, poly alcohols, water), creams, lotions, ointments, oils, plasters, liposomes, powders, emulsions, microemulsions, and buffered solutions (e.g., hypotonic or buffered saline) or any other carrier known in the art for topically administering pharmaceuticals. A more complete listing of art-known carriers is provided by reference texts that are standard in the art, for example, Remington's Pharmaceutical Sciences, 16th Edition, 1980 and 17th Edition, 1985, both published by Mack Publishing Company, Easton, Pa., the disclosures of which are incorporated herein by reference in their entireties. In certain other embodiments, the topical formulations of the invention may comprise excipients. Any pharmaceutically acceptable excipient known in the art may be used to prepare the inventive pharmaceutically acceptable topical formulations. Examples of excipients that can be included in the topical formulations of the invention include, but are not limited to, preservatives, antioxidants, moisturizers, emollients, buffering agents, solubilizing agents, other penetration agents, skin protectants, surfactants, and propellants, and/or additional therapeutic agents used in combination to the inventive compound. Suitable preservatives include, but are not limited to, alcohols, quaternary amines, organic acids, parabens, and phenols. Suitable antioxidants include, but are not limited to, ascorbic acid and its esters, sodium bisulfite, butylated hydroxytoluene, butylated hydroxyanisole, tocopherols, and chelating agents like EDTA and citric acid. Suitable moisturizers include, but are not limited to, glycerine, sorbitol, polyethylene glycols, urea, and propylene glycol. Suitable buffering agents for use with the invention include, but are not limited to, citric, hydrochloric, and lactic acid buffers. Suitable solubilizing agents include, but are not limited to, quaternary ammonium chlorides, cyclodextrins, benzyl benzoate, lecithin, and polysorbates. Suitable skin protectants that can be used in the topical formulations of the invention include, but are not limited to, vitamin E oil, allatoin, dimethicone, glycerin, petrolatum, and zinc oxide.
In certain embodiments, the pharmaceutically acceptable topical formulations of the invention comprise at least a compound of the invention and a penetration enhancing agent. The choice of topical formulation will depend or several factors, including the condition to be treated, the physicochemical characteristics of the inventive compound and other excipients present, their stability in the formulation, available manufacturing equipment, and costs constraints. As used herein the term “penetration enhancing agent” means an agent capable of transporting a pharmacologically active compound through the stratum corneum and into the epidermis or dermis, preferably, with little or no systemic absorption. A wide variety of compounds have been evaluated as to their effectiveness in enhancing the rate of penetration of drugs through the skin. See, for example, Percutaneous Penetration Enhancers , Maibach H. I. and Smith H. E. (eds.), CRC Press, Inc., Boca Raton, Fla. (1995), which surveys the use and testing of various skin penetration enhancers, and Buyuktimkin et al., Chemical Means of Transdermal Drug Permeation Enhancement in Transdermal and Topical Drug Delivery Systems, Gosh T. K., Pfister W. R., Yum S. I. (Eds.), Interpharm Press Inc., Buffalo Grove, Ill. (1997). In certain exemplary embodiments, penetration agents for use with the invention include, but are not limited to, triglycerides (e.g., soybean oil), aloe compositions (e.g., aloe-vera gel), ethyl alcohol, isopropyl alcohol, octolyphenylpolyethylene glycol, oleic acid, polyethylene glycol 400, propylene glycol, N-decylmethylsulfoxide, fatty acid esters (e.g., isopropyl myristate, methyl laurate, glycerol monooleate, and propylene glycol monooleate), and N-methylpyrrolidone.
In certain embodiments, the compositions may be in the form of ointments, pastes, creams, lotions, gels, powders, solutions, sprays, inhalants or patches. In certain exemplary embodiments, formulations of the compositions according to the invention are creams, which may further contain saturated or unsaturated fatty acids such as stearic acid, palmitic acid, oleic acid, palmito-oleic acid, cetyl or oleyl alcohols, stearic acid being particularly preferred. Creams of the invention may also contain a non-ionic surfactant, for example, polyoxy-40-stearate. In certain embodiments, the active component is admixed under sterile conditions with a pharmaceutically acceptable carrier and any needed preservatives or buffers as may be required. Ophthalmic formulation, eardrops, and eye drops are also contemplated as being within the scope of this invention. Additionally, the present invention contemplates the use of transdermal patches, which have the added advantage of providing controlled delivery of a compound to the body. Such dosage forms are made by dissolving or dispensing the compound in the proper medium. As discussed above, penetration enhancing agents can also be used to increase the flux of the compound across the skin. The rate can be controlled by either providing a rate controlling membrane or by dispersing the compound in a polymer matrix or gel.
It will also be appreciated that the compounds and pharmaceutical compositions of the present invention can be formulated and employed in combination therapies, that is, the compounds and pharmaceutical compositions can be formulated with or administered concurrently with, prior to, or subsequent to, one or more other desired therapeutics or medical procedures. The particular combination of therapies (therapeutics or procedures) to employ in a combination regimen will take into account compatibility of the desired therapeutics and/or procedures and the desired therapeutic effect to be achieved. It will also be appreciated that the therapies employed may achieve a desired effect for the same disorder (for example, an inventive compound may be administered concurrently with another immunomodulatory agent, anticancer agent or agent useful for the treatment of psoriasis), or they may achieve different effects (e.g., control of any adverse effects).
For example, other therapies or anticancer agents that may be used in combination with the inventive compounds of the present invention include surgery, radiotherapy (in but a few examples, γ-radiation, neutron beam radiotherapy, electron beam radiotherapy, proton therapy, brachytherapy, and systemic radioactive isotopes, to name a few), endocrine therapy, biologic response modifiers (interferons, interleukins, and tumor necrosis factor (TNF) to name a few), hyperthermia and cryotherapy, agents to attenuate any adverse effects (e.g., antiemetics), and other approved chemotherapeutic drugs, including, but not limited to, alkylating drugs (mechlorethamine, chlorambucil, Cyclophosphamide, Melphalan, Ifosfamide), antimetabolites (Methotrexate), purine antagonists and pyrimidine antagonists (6-Mercaptopurine, 5-Fluorouracil, Cytarabile, Gemcitabine), spindle poisons (Vinblastine, Vincristine, Vinorelbine, Paclitaxel), podophyllotoxins (Etoposide, Irinotecan, Topotecan), antibiotics (Doxorubicin, Bleomycin, Mitomycin), nitrosoureas (Carmustine, Lomustine), inorganic ions (Cisplatin, Carboplatin), enzymes (Asparaginase), and hormones (Tamoxifen, Leuprolide, Flutamide, and Megestrol), to name a few. For a more comprehensive discussion of updated cancer therapies see, The Merck Manual , Seventeenth Ed. 1999, the entire contents of which are hereby incorporated by reference. See also the National Cancer Institute (CNI) website (www.nci.nih.gov) and the Food and Drug Administration (FDA) website for a list of the FDA approved oncology drugs (www.fda.gov/cder/cancer/druglistframe).
In certain embodiments, the pharmaceutical compositions of the present invention further comprise one or more additional therapeutically active ingredients (e.g., chemotherapeutic and/or palliative). For purposes of the invention, the term “palliative” refers to treatment that is focused on the relief of symptoms of a disease and/or side effects of a therapeutic regimen, but is not curative. For example, palliative treatment encompasses painkillers, antinausea medications and anti-sickness drugs. In addition, chemotherapy, radiotherapy and surgery can all be used palliatively (that is, to reduce symptoms without going for cure; e.g., for shrinking tumors and reducing pressure, bleeding, pain and other symptoms of cancer).
Additionally, the present invention provides pharmaceutically acceptable derivatives of the inventive compounds, and methods of treating a subject using these compounds, pharmaceutical compositions thereof, or either of these in combination with one or more additional therapeutic agents.
It will also be appreciated that certain of the compounds of present invention can exist in free form for treatment, or where appropriate, as a pharmaceutically acceptable derivative thereof. According to the present invention, a pharmaceutically acceptable derivative includes, but is not limited to, pharmaceutically acceptable salts, esters, salts of such esters, or a prodrug or other adduct or derivative of a compound of this invention which upon administration to a patient in need is capable of providing, directly or indirectly, a compound as otherwise described herein, or a metabolite or residue thereof.
Research Uses, Pharmaceutical Uses and Methods of Treatment
Research Uses
According to the present invention, the inventive compounds may be assayed in any of the available assays known in the art for identifying compounds having antiprotozoal, HDAC inhibitory, hair growth, androgen signalling inhibitory, estogen singaling inhibitory, and/or antiproliferative activity. For example, the assay may be cellular or non-cellular, in vivo or in vitro, high-or low-throughput format, etc.
Thus, in one aspect, compounds of this invention which are of particular interest include those which:
exhibit HDAC-inhibitory activity; exhibit HDAC Class I inhbitiory activity (e.g., HDAC1, HDAC2, HDAC3, HDAC8); exhibit HDAC Class II inhibitory activity (e.g., HDAC4, HDAC5, HDAC6, HDAC7, HDAC9a, HDAC9b, HDRP/HDAC9c, HDAC10); exhibit the ability to inhibit HDAC1 (Genbank Accession No. NP — 004955, incorporated herein by reference); exhibit the ability to inhibit HDAC2 (Genbank Accession No. NP — 001518, incorporated herein by reference); exhibit the ability to inhibit HDAC3 (Genbank Accession No. O15739, incorporated herein by reference); exhibit the ability to inhibit HDAC4 (Genbank Accession No. AAD29046, incorporated herein by reference); exhibit the ability to inhibit HDAC5 (Genbank Accession No. NP — 005465, incorporated herein by reference); exhibit the ability to inhibit HDAC6 (Genbank Accession No. NP — 006035, incorporated herein by reference); exhibit the ability to inhibit HDAC7 (Genbank Accession No. AAP63491, incorporated herein by reference); exhibit the ability to inhibit HDAC8 (Genbank Accession No. AAF73428, NM — 018486, AF245664, AF230097, each of which is incorporated herein by reference); exhibit the ability to inhibit HDAC9 (Genbank Accession No. NM — 178425, NM — 178423, NM — 058176, NM — 014707, BC111735, NM — 058177, each of which is incorporated herein by reference) exhibit the ability to inhibit HDAC10 (Genbank Accession No. NM — 032019, incorporated herein by reference) exhibit the ability to inhibit HDAC11 (Genbank Accession No. BC009676, incorporated herein by reference); exhibit the ability to inhibit tubulin deactetylation (TDAC); exhibit the ability to modulate the glucose-sensitive subset of genes downstream of Ure2p; exhibit cytotoxic or growth inhibitory effect on cancer cell lines maintained in vitro or in animal studies using a scientifically acceptable cancer cell xenograft model; and/or exhibit a therapeutic profile (e.g., optimum safety and curative effect) that is superior to existing chemotherapeutic agents.
As detailed in the exemplification herein, in assays to determine the ability of compounds to inhibit cancer cell growth certain inventive compounds may exhibit IC 50 values ≦100 μM. In certain other embodiments, inventive compounds exhibit IC 50 values ≦50 μM. In certain other embodiments, inventive compounds exhibit IC 50 values ≦40 μM. In certain other embodiments, inventive compounds exhibit IC 50 values ≦30 μM. In certain other embodiments, inventive compounds exhibit IC 50 values ≦20 μM. In certain other embodiments, inventive compounds exhibit IC 50 values ≦10 μM. In certain other embodiments, inventive compounds exhibit IC 50 values ≦7.5 μM. In certain embodiments, inventive compounds exhibit IC 50 values ≦5 μM. In certain other embodiments, inventive compounds exhibit IC 50 values ≦2.5 μM. In certain embodiments, inventive compounds exhibit IC 50 values ≦1 μM. In certain embodiments, inventive compounds exhibit IC 50 values ≦0.75 μM. In certain embodiments, inventive compounds exhibit IC 50 values ≦0.5 μM. In certain embodiments, inventive compounds exhibit IC 50 values ≦0.25 μM. In certain embodiments, inventive compounds exhibit IC 50 values ≦0.1 μM. In certain other embodiments, inventive compounds exhibit IC 50 values ≦75 nM. In certain other embodiments, inventive compounds exhibit IC 50 values ≦50 nM. In certain other embodiments, inventive compounds exhibit IC 50 values ≦25 nM. In certain other embodiments, inventive compounds exhibit IC 50 values ≦10 nM. In other embodiments, exemplary compounds exhibited IC 50 values ≦7.5 nM. In other embodiments, exemplary compounds exhibited IC 50 values ≦5 nM.
Pharmaceutical Uses and Methods of Treatment
In general, methods of using the compounds of the present invention comprise administering to a subject in need thereof a therapeutically effective amount of a compound of the present invention. The compounds of the invention are generally inhibitors of deacetyalse activity. As discussed above, the compounds of the invention are typically inhibitors of histone deacetylases and, as such, are useful in the treatment of disorders modulated by histone deacetylases. Other deacetylase such as tubulin deacetylases may also be inhibited by the inventive compounds.
In certain embodiments, compounds of the invention are useful in the treatment of proliferative diseases (e.g., cancer, benign neoplasms, inflammatory disease, autoimmune diseases). In certain embodiments, given the esterase sensitive ester linkage in the compounds of the invention, they are particularly useful in treating skin disorders modulated by histone deacetyalses where systemic effects of the drug are to be avoided or at least minimized. This feature of the inventive compounds may allow the use of compounds normally too toxic for administration to a subject systemically. In certain embodiments, these skin disorders are proliferative disorders. For example, the inventive compounds are particularly useful in the treatment of skin cancer and benign skin tumors. In certain embodiments, the compounds are useful in the treatment of cutaneous T-cell lymphoma. In certain embodiments, the compounds are useful in the treatment of neurofibromatosis. Accordingly, in yet another aspect, according to the methods of treatment of the present invention, tumor cells are killed, or their growth is inhibited by contacting said tumor cells with an inventive compound or composition, as described herein. In other embodiments, the compounds are useful in treating inflammatory diseases of the skin such as psoriasis or dermatitis. In other embodiments, the compounds are useful in the treatment or prevention of hair loss. In certain embodiments, the compounds are useful in the treatment of diseases associated with skin pigmentation. For example, the compounds may be used to prevent the hyperpigmentation of skin.
Thus, in another aspect of the invention, methods for the treatment of cancer are provided comprising administering a therapeutically effective amount of an inventive compound, as described herein, to a subject in need thereof. In certain embodiments, a method for the treatment of cancer is provided comprising administering a therapeutically effective amount of an inventive compound, or a pharmaceutical composition comprising an inventive compound to a subject in need thereof, in such amounts and for such time as is necessary to achieve the desired result. Preferably, the inventive compounds is administered topically. In certain embodiments of the present invention a “therapeutically effective amount” of the inventive compound or pharmaceutical composition is that amount effective for killing or inhibiting the growth of tumor cells. The compounds and compositions, according to the method of the present invention, may be administered using any amount and any route of administration effective for killing or inhibiting the growth of tumor cells. Thus, the expression “amount effective to kill or inhibit the growth of tumor cells,” as used herein, refers to a sufficient amount of agent to kill or inhibit the growth of tumor cells. The exact amount required will vary from subject to subject, depending on the species, age, and general condition of the subject, the severity of the infection, the particular anticancer agent, its mode of administration, and the like. In certain embodiments of the present invention a “therapeutically effective amount” of the inventive compound or pharmaceutical composition is that amount effective for inhibiting deacetylase activity (in particular, HDAC activity) in skin cells. In certain embodiments of the present invention a “therapeutically effective amount” of the inventive compound or pharmaceutical composition is that amount effective to kill or inhibit the growth of skin cells.
In certain embodiments, the method involves the administration of a therapeutically effective amount of the compound or a pharmaceutically acceptable derivative thereof to a subject (including, but not limited to a human or animal) in need of it. In certain embodiments, the inventive compounds as useful for the treatment of cancer (including, but not limited to, glioblastoma, retinoblastoma, breast cancer, cervical cancer, colon and rectal cancer, leukemia, lymphoma, lung cancer (including, but not limited to small cell lung cancer), melanoma and/or skin cancer, multiple myeloma, non-Hodgkin's lymphoma, ovarian cancer, pancreatic cancer, prostate cancer and gastric cancer, bladder cancer, uterine cancer, kidney cancer, testicular cancer, stomach cancer, brain cancer, liver cancer, or esophageal cancer).
In certain embodiments, the inventive anticancer agents are useful in the treatment of cancers and other proliferative disorders, including, but not limited to breast cancer, cervical cancer, colon and rectal cancer, leukemia, lung cancer, melanoma, multiple myeloma, non-Hodgkin's lymphoma, ovarian cancer, pancreatic cancer, prostate cancer, and gastric cancer, to name a few. In certain embodiments, the inventive anticancer agents are active against leukemia cells and melanoma cells, and thus are useful for the treatment of leukemias (e.g., myeloid, lymphocytic, myelocytic and lymphoblastic leukemias) and malignant melanomas. In still other embodiments, the inventive anticancer agents are active against solid tumors.
In certain embodiments, the inventive compounds also find use in the prevention of restenosis of blood vessels subject to traumas such as angioplasty and stenting. For example, it is contemplated that the compounds of the invention will be useful as a coating for implanted medical devices, such as tubings, shunts, catheters, artificial implants, pins, electrical implants such as pacemakers, and especially for arterial or venous stents, including balloon-expandable stents. In certain embodiments inventive compounds may be bound to an implantable medical device, or alternatively, may be passively adsorbed to the surface of the implantable device. In certain other embodiments, the inventive compounds may be formulated to be contained within, or, adapted to release by a surgical or medical device or implant, such as, for example, stents, sutures, indwelling catheters, prosthesis, and the like. For example, drugs having antiproliferative and anti-inflammatory activities have been evaluated as stent coatings, and have shown promise in preventing retenosis (See, for example, Presbitero P. et al., “Drug eluting stents do they make the difference?”, Minerva Cardioangiol, 2002, 50(5):431-442; Ruygrok P. N. et al., “Rapamycin in cardiovascular medicine”, Intern. Med. J., 2003, 33(3):103-109; and Marx S. O. et al., “Bench to bedside: the development of rapamycin and its application to stent restenosis”, Circulation, 2001, 104(8):852-855, each of these references is incorporated herein by reference in its entirety). Accordingly, without wishing to be bound to any particular theory, Applicant proposes that inventive compounds having antiproliferative effects can be used as stent coatings and/or in stent drug delivery devices, inter alia for the prevention of restenosis or reduction of restenosis rate. Suitable coatings and the general preparation of coated implantable devices are described in U.S. Pat. Nos. 6,099,562; 5,886,026; and 5,304,121. The coatings are typically biocompatible polymeric materials such as a hydrogel polymer, polymethyldisiloxane, polycaprolactone, polyethylene glycol, polylactic acid, ethylene vinyl acetate, and mixtures thereof. The coatings may optionally be further covered by a suitable topcoat of fluorosilicone, polysaccarides, polyethylene glycol, phospholipids or combinations thereof to impart controlled release characteristics in the composition. A variety of compositions and methods related to stent coating and/or local stent drug delivery for preventing restenosis are known in the art (see, for example, U.S. Pat. Nos. 6,517,889; 6,273,913; 6,258,121; 6,251,136; 6,248,127; 6,231,600; 6,203,551; 6,153,252; 6,071,305; 5,891,507; 5,837,313 and published U.S. patent application No.: US2001/0027340, each of which is incorporated herein by reference in its entirety). For example, stents may be coated with polymer-drug conjugates by dipping the stent in polymer-drug solution or spraying the stent with such a solution. In certain embodiment, suitable materials for the implantable device include biocompatible and nontoxic materials, and may be chosen from the metals such as nickel-titanium alloys, steel, or biocompatible polymers, hydrogels, polyurethanes, polyethylenes, ethylenevinyl acetate copolymers, etc. In certain embodiments, the inventive compound is coated onto a stent for insertion into an artery or vein following balloon angioplasty.
The compounds of this invention or pharmaceutically acceptable compositions thereof may also be incorporated into compositions for coating implantable medical devices, such as prostheses, artificial valves, vascular grafts, stents and catheters. Accordingly, the present invention, in another aspect, includes a composition for coating an implantable device comprising a compound of the present invention as described generally above, and in classes and subclasses herein, and a carrier suitable for coating said implantable device. In still another aspect, the present invention includes an implantable device coated with a composition comprising a compound of the present invention as described generally above, and in classes and subclasses herein, and a carrier suitable for coating said implantable device.
Within other aspects of the present invention, methods are provided for expanding the lumen of a body passageway, comprising inserting a stent into the passageway, the stent having a generally tubular structure, the surface of the structure being coated with (or otherwise adapted to release) an inventive compound or composition, such that the passageway is expanded. In certain embodiments, the lumen of a body passageway is expanded in order to eliminate a biliary, gastrointestinal, esophageal, tracheal/bronchial, urethral and/or vascular obstruction.
Methods for eliminating biliary, gastrointestinal, esophageal, tracheal/bronchial, urethral and/or vascular obstructions using stents are known in the art. The skilled practitioner will know how to adapt these methods in practicing the present invention. For example, guidance can be found in U.S. Patent Application Publication No.: 2003/0004209 in paragraphs [0146]-[0155], which paragraphs are hereby incorporated herein by reference.
Another aspect of the invention relates to a method for inhibiting the growth of multidrug resistant cells in a biological sample or a patient, which method comprises administering to the patient, or contacting said biological sample with a compound of formula I or a composition comprising said compound.
Additionally, the present invention provides pharmaceutically acceptable derivatives of the inventive compounds, and methods of treating a subject using these compounds, pharmaceutical compositions thereof, or either of these in combination with one or more additional therapeutic agents.
Another aspect of the invention relates to a method of treating or lessening the severity of a disease or condition associated with a proliferation disorder in a patient, said method comprising a step of administering to said patient, a compound of formula I or a composition comprising said compound.
It will be appreciated that the compounds and compositions, according to the method of the present invention, may be administered using any amount and any route of administration effective for the treatment of cancer and/or disorders associated with cell hyperproliferation. For example, when using the inventive compounds for the treatment of cancer, the expression “effective amount” as used herein, refers to a sufficient amount of agent to inhibit cell proliferation, or refers to a sufficient amount to reduce the effects of cancer. The exact amount required will vary from subject to subject, depending on the species, age, and general condition of the subject, the severity of the diseases, the particular anticancer agent, its mode of administration, and the like.
The compounds of the invention are preferably formulated in dosage unit form for ease of administration and uniformity of dosage. The expression “dosage unit form” as used herein refers to a physically discrete unit of therapeutic agent appropriate for the patient to be treated. It will be understood, however, that the total daily usage of the compounds and compositions of the present invention will be decided by the attending physician within the scope of sound medical judgment. The specific therapeutically effective dose level for any particular patient or organism will depend upon a variety of factors including the disorder being treated and the severity of the disorder; the activity of the specific compound employed; the specific composition employed; the age, body weight, general health, sex and diet of the patient; the time of administration, route of administration, and rate of excretion of the specific compound employed; the duration of the treatment; drugs used in combination or coincidental with the specific compound employed; and like factors well known in the medical arts (see, for example, Goodman and Gilman's, “The Pharmacological Basis of Therapeutics”, Tenth Edition, A. Gilman, J. Hardman and L. Limbird, eds., McGraw-Hill Press, 155-173, 2001, which is incorporated herein by reference in its entirety).
Another aspect of the invention relates to a method for inhibiting histone deacetylase activity in a biological sample or a patient, which method comprises administering to the patient, or contacting said biological sample with an inventive compound or a composition comprising said compound.
Furthermore, after formulation with an appropriate pharmaceutically acceptable carrier in a desired dosage, the pharmaceutical compositions of this invention can be administered to humans and other animals orally, rectally, parenterally, intracisternally, intravaginally, intraperitoneally, topically (as by powders, ointments, creams or drops), bucally, as an oral or nasal spray, or the like, depending on the severity of the infection being treated. In certain embodiments, the compounds of the invention may be administered at dosage levels of about 0.001 mg/kg to about 50 mg/kg, from about 0.01 mg/kg to about 25 mg/kg, or from about 0.1 mg/kg to about 10 mg/kg of subject body weight per day, one or more times a day, to obtain the desired therapeutic effect. It will also be appreciated that dosages smaller than 0.001 mg/kg or greater than 50 mg/kg (for example 50-100 mg/kg) can be administered to a subject. In certain embodiments, compounds are administered orally or parenterally.
Treatment Kit
In other embodiments, the present invention relates to a kit for conveniently and effectively carrying out the methods in accordance with the present invention. In general, the pharmaceutical pack or kit comprises one or more containers filled with one or more of the ingredients of the pharmaceutical compositions of the invention. Such kits are especially suited for the topical delivery of the inventive compounds. Optionally associated with such container(s) can be a notice in the form prescribed by a governmental agency regulating the manufacture, use or sale of pharmaceutical products, which notice reflects approval by the agency of manufacture, use or sale for human administration.
Equivalents
The representative examples which follow are intended to help illustrate the invention, and are not intended to, nor should they be construed to, limit the scope of the invention. Indeed, various modifications of the invention and many further embodiments thereof, in addition to those shown and described herein, will become apparent to those skilled in the art from the full contents of this document, including the examples which follow and the references to the scientific and patent literature cited herein. It should further be appreciated that, unless otherwise indicated, the entire contents of each of the references cited herein are incorporated herein by reference to help illustrate the state of the art. The following examples contain important additional information, exemplification and guidance which can be adapted to the practice of this invention in its various embodiments and the equivalents thereof.
These and other aspects of the present invention will be further appreciated upon consideration of the following Examples, which are intended to illustrate certain particular embodiments of the invention but are not intended to limit its scope, as defined by the claims.
EXAMPLES
The compounds of this invention and their preparation can be understood further by the examples that illustrate some of the processes by which these compounds are prepared or used. Tt will be appreciated, however, that these examples do not limit the invention. Variations of the invention, now known or further developed, are considered to fall within the scope of the present invention as described herein and as hereinafter claimed.
General Description of Synthetic Methods
The various references cited herein provide helpful background information on preparing compounds similar to the inventive compounds described herein or relevant intermediates, as well as information on formulation, uses, and administration of such compounds which may be of interest.
Moreover, the practitioner is directed to the specific guidance and examples provided in this document relating to various exemplary compounds and intermediates thereof.
The compounds of this invention and their preparation can be understood further by the examples that illustrate some of the processes by which these compounds are prepared or used. It will be appreciated, however, that these examples do not limit the invention. Variations of the invention, now known or further developed, are considered to fall within the scope of the present invention as described herein and as hereinafter claimed.
According to the present invention, any available techniques can be used to make or prepare the inventive compounds or compositions including them. For example, a variety of a variety combinatorial techniques, parallel synthesis and/or solid phase synthetic methods such as those discussed in detail below may be used. Alternatively or additionally, the inventive compounds may be prepared using any of a variety of solution phase synthetic methods known in the art.
It will be appreciated as described below, that a variety of inventive compounds can be synthesized according to the methods described herein. The starting materials and reagents used in preparing these compounds are either available from commercial suppliers such as Aldrich Chemical Company (Milwaukee, Wis.), Bachem (Torrance, Calif.), Sigma (St. Louis, Mo.), or are prepared by methods well known to a person of ordinary skill in the art following procedures described in such references as Fieser and Fieser 1991, “Reagents for Organic Synthesis”, vols 1-17, John Wiley and Sons, New York, N.Y., 1991; Rodd 1989 “Chemistry of Carbon Compounds”, vols. 1-5 and supps, Elsevier Science Publishers, 1989; “Organic Reactions”, vols 1-40, John Wiley and Sons, New York, N.Y., 1991; March 2001, “Advanced Organic Chemistry”, 5th ed. John Wiley and Sons, New York, N.Y.; and Larock 1990, “Comprehensive Organic Transformations: A Guide to Functional Group Preparations”, 2 nd ed. VCH Publishers. These schemes are merely illustrative of some methods by which the compounds of this invention can be synthesized, and various modifications to these schemes can be made and will be suggested to a person of ordinary skill in the art having regard to this disclosure.
The starting materials, intermediates, and compounds of this invention may be isolated and purified using conventional techniques, including filtration, distillation, crystallization, chromatography, and the like. They may be characterized using conventional methods, including physical constants and spectral data.
Synthesis of Exemplary Compounds
Unless otherwise indicated, starting materials are either commercially available or readily accessibly through laboratory synthesis by anyone reasonably familiar with the art. Described generally below, are procedures and general guidance for the synthesis of compounds as described generally and in subclasses and species herein.
Example 1
Synthesis of SAB for Use as HDAC Inhibitors
Described below is the synthesis of a SAHP, an ester-containing analog of SAHA (as shown in FIG. 12 ).
3.86 g (24.2 mmol) O-benzylhydroxylamine hydrochloride and 13 mL (75 mmol) diisopropylethylamine were dissolved in 100 mL methylene chloride and cooled to 0° C. 5.00 g (24.2 mmol) methyl 8-chloro-8-oxooctanoate were dissolved in 10 mL methylene chloride and slowly added to the reaction mixture. The reaction mixture was stirred for 1 h at 0° C. and warmed to room temperature. After stirring for additional 12 h, 300 mL 0.5N HCl were added. The organic layer was separated and washed with brine and sat. bicarb. After drying over sodium sulfate, the organic solvent was removed under reduced pressure and the crude product was purified on silica (methylene chloride/methanol 12:1, r=0.7) to yield the desired compound 1 as white solid (6.3 g, 89%).
6.3 g (21.5 mmol) methyl ester 1 were dissolved in 200 mL methanol, followed by the addition of 50 mL 2N LiOH. The reaction mixture was heated to reflux for 1 h and cooled to room temperature. After addition of 100 mL 1N HCl and 200 mL water, the reaction mixture was extracted three times with 150 mL ethyl acetate. The combined organic layers were dried over sodium sulfate and the solvent was removed under reduced pressure to afford the carboxylic acid 2 pure and in quantitative yields as white solid
140 mg carboxylic acid 2 (5 mmol), 56.5 mg phenol (6 mmol) and 113 mg dicyclohexylcarbodiimide (5.5 mmol) are mixed followed by the addition of 10 mL methylene chloride and 30 mg 4-Dimethylaminopyridine. The reaction mixture was stirred for 2 h and applied crude on a silica column followed by elution with haxanes/ethyl acetate (10-100% ethyl acetate). The desired phenol ester 3 was obtained as a white solid in 87% yield (155 mg).
80 mg phenol ester 3 (0.225 mmol) are dissolved in methanol. A catalytical amount of palladium on charcoal (10%) was as added and hydrogen was bubbled through the reaction mixture. After 1 h hour no starting material was detectable by TLC. The reaction mixture was filtered through Celite and the solvent was removed under reduced pressure to yield the free hydroxamte SAHP as brownish solid in quantitative yields (59 mg). The crude product did not show any impurities as judged by LCMS and NMR.
Example 2
Biological Assay Procedures
Cell culture and Transfections. TAg-Jurkat cells were transfected by electroporation with 5 μg of FLAG-epitope-tagged pBJ5 constructs for expression of recombinant proteins. Cells were harvested 48 h posttransfection.
HDAC assays. [ 3 H]Acetate-incorporated histones were isolated from butyrate-treated HeLa cells by hydroxyapatite chromatography (as described in Tong, et al Nature 1997, 395, 917-921.) Immunoprecipitates were incubated with 1.4 μg (10,000 dpm) histones for 3 h at 37° C. HDAC activity was determined by scintillation counting of the ethyl acetate-soluble [ 3 H]acetic acid (as described in Taunton, et al., Science 1996, 272, 408-411). Compounds were added in DMSO such that final assay concentrations were 1% DMSO. IC50s were calculated using Prism 3.0 software. Curve fitting was done without constraints using the program's Sigmoidal-Dose Response parameters. All data points were acquired in duplicate and IC50s are calculated from the composite results of at least two separate experiments.
Example 3
In Vivo Activity
Although a variety of methods can be utilized, one exemplary method by which the in vivo activity of the inventive compounds is determined is by subcutaneously transplanting a desired tumor mass in mice. Drug treatment is then initiated when tumor mass reaches approximately 100 mm 3 after transplantation of the tumor mass. A suitable composition, as described in more detail above, is then administered to the mice, preferably in saline and also preferably administered once a day at doses of 5, 10 and 25 mg/kg, although it will be appreciated that other doses can also be administered. Body weight and tumor size are then measured daily and changes in percent ratio to initial values are plotted. In cases where the transplanted tumor ulcerates, the weight loss exceeds 25-30% of control weight loss, the tumor weight reaches 10% of the body weight of the cancer-bearing mouse, or the cancer-bearing mouse is dying, the animal is sacrificed in accordance with guidelines for animal welfare.
Example 4
Assays to Identify Potential Antiprotozoal Compounds by Inhibition of Histone Deacetylase
As detailed in U.S. Pat. No. 6,068,987, inhibitors of histone deacetylases may also be useful as antiprotozoal agents. Described therein are assays for histone deacetylase activity and inhibition and describe a variety of known protozoal diseases. The entire contents of U.S. Pat. No. 6,068,987 are hereby incorporated by reference. | In recognition of the need to develop novel therapeutic agents, the present invention provides novel histone deacetylase inhibitors. These compounds include an ester bond making them sensitive to deactivation by esterases. Therefore, these compounds are particularly useful in the treatment of skin disorders. When the compounds reaches the bloodstream, an esterase or an enzyme with esterase activity cleaves the compound into biologically inactive fragments or fragments with greatly reduced activity Ideally these degradation products exhibit a short serum and/or systemic half-life and are eliminated rapidly. These compounds and pharmaceutical compositions thereof are particularly useful in treating cutaneous T-cell lymphoma, neurofibromatosis, psoriasis, hair loss, skin pigmentation, and dermatitis, for example. The present invention also provides methods for preparing compounds of the invention and intermediates thereto. | 2 |
BACKGROUND
The present invention is directed to locking hydraulic actuators and a method for locking a hydraulic actuator in a predetermined position.
Locking hydraulic actuators are commonly used in situations where it is desirable to have a hydraulic actuator which can be secured in a predetermined position without the necessity of maintaining the presence of hydraulic supply pressure. Locking hydraulic actuators are commonly used, for example, in the aircraft industry for lowering or raising landing gear. All prior art locking actuators utilize some sort of internal mechanical locking means. For example, most modern prior art locking actuators utilize a plurality of radially moving locking members which engage into a groove to lock the hydraulic actuator in a predetermined position. These generally contain a shear element physically wedged between the stationary actuator cylinder and the moving piston. Dynamic loads reacted to by relatively small metal to metal contact areas induce large stress concentrations within the locking members and are thus subject to premature wear.
Accordingly, there is a need for a locking hydraulic actuator that is structurally simple, easy and inexpensive to manufacture, durable, and which distribute the locking load both uniformly and symmetrically.
SUMMARY
This invention satisfies this need. The present invention is a method and a locking hydraulic actuator for locking the piston of a hydraulic actuator in a predetermined position without relying on mechanical locking means.
The invention is a method for locking a hydraulic actuator in a predetermined position comprising the steps of (1) supplying hydraulic fluid from a source of hydraulic fluid into a forward chamber disposed in the actuator enclosure, (2) transferring the hydraulic fluid from the forward chamber into a forward moiety of a rearward chamber disposed in the actuator enclosure, and (3) sealing the hydraulic fluid in the forward moiety of the rearward chamber. The forward chamber is defined by the forward end wall, the actuator enclosure, the piston rod, and an intermediate wall positioned between the forward end wall and the piston. The forward moiety of the rearward chamber is defined by the piston, the piston rod, the actuator enclosure, and the intermediate wall.
The hydraulic fluid is sealed in the forward moiety of the rearward chamber by closing an internal valve device. The hydraulic fluid can be transferred from the forward chamber to the forward moiety of the rearward chamber through a cavity in the piston rod, and the valve device can be slidably disposed in the cavity in the piston rod.
The method can further comprise the step of relieving hydraulic pressure in the forward moiety of the rearward chamber created by the thermal expansion of the hydraulic fluid when the actuator is in the locked mode. In this embodiment, thermal expansion of the hydraulic fluid will not result in excessive fluid pressures within the locked chamber.
The invention is also a locking hydraulic actuator comprising a housing member, a piston, a piston seal, a piston rod, an intermediate piston rod seal, a forward piston rod seal, a first port, a second port, a fluid passageway, and a valve device.
The housing member can be a hollow cylinder bounded by a forward end wall and a rearward end wall. The forward end wall and the rearward end wall cooperate with the hollow cylinder to define an actuator enclosure having an interior surface. The housing member has an intermediate wall disposed within the actuator enclosure between the forward end wall and the rearward end wall so as to partition the actuator enclosure into a forward chamber and a rearward chamber. The rearward chamber has a forward moiety and a rearward moiety, and the forward end wall and the intermediate wall each have a central aperture.
The piston has a forward facing surface, a rearward facing surface, and a cross-sectional shape which corresponds to that of the actuator enclosure. The piston is sized and dimensioned to closely conform to the interior surface of the actuator enclosure. Additionally, the piston is slidably disposed within the rearward chamber and partitions the rearward chamber into a forward moiety and a rearward moiety. The size of the forward and rearward moieties change as the piston moves within the actuator enclosure.
The piston seal slidably seals the piston to the interior surface of the actuating enclosure. The piston seal prevents the flow of hydraulic fluid between the piston and the interior surface of the actuator enclosure.
The piston rod is attached to the forward end of the piston and extends away from the piston through the central apertures in the intermediate wall and the forward end wall. The piston rod is attached and is moved by the piston. For example, when sufficient pressure is applied to the rearward facing surface of the piston, the piston moves toward the intermediate wall and the piston rod extends away from the forward end wall. Alternatively, when sufficient pressure is applied to the forward facing surface of the piston, the piston moves toward the rearward end wall and the piston rod is retracted into the hydraulic actuator.
The intermediate piston rod seal slidably seals the piston rod to the central aperture in the intermediate wall and the forward piston rod seal slidably seals the piston rod to the central aperture in the forward end wall. Each of these seals prevents the flow of hydraulic fluid between the piston rod and the central aperture in each respective wall.
The first port is disposed in the housing member to permit fluid communication between the forward chamber and either a source of pressurized hydraulic fluid or an external return sump. Similarly, the second part is disposed in the housing member to permit fluid communication between the rearward moiety of the rearward chamber and either a source of pressurized hydraulic fluid or an external return sump. Basically, the source of pressurized hydraulic fluid can be supplied to the forward chamber through the first port and the source of pressurized hydraulic fluid can be supplied to the rearward moiety of the rearward chamber through the second port.
The fluid passageway connects the forward chamber and the forward moiety of the rearward chamber in fluid communication. Basically, the fluid passageway allows for the flow of hydraulic fluid between the forward chamber and the forward moiety of the rearward chamber.
The valve device is a device disposed in the fluid passageway for alternatively closing and opening the fluid passageway to fluid flow between the forward chamber and the forward moiety of the rearward chamber. When the valve device is open, hydraulic fluid can flow between the forward chamber and the forward moiety of the rearward chamber. Alternatively, when the valve device is closed, the fluid passageway is closed, and hydraulic fluid flow between the forward chamber and the forward moiety of the rearward chamber is blocked. Thus, when the valve device is closed, the forward moiety of the rearward chamber becomes a sealed chamber containing hydraulic fluid. The hydraulic fluid sealed in the forward moiety of the rearward chamber, when the valve device is closed, holds the piston in the locked position.
Preferably, the actuator enclosure of the housing member has a circular cross section and the piston has the shape of a right circular cylinder, to facilitate manufacturing of the actuator and the use of standard seals.
The hydraulic actuator can include a pressure relief valve for releasing hydraulic fluid from the forward moiety of the rearward chamber into the forward chamber when the pressure of the hydraulic fluid in the forward moiety of the rearward chamber reaches a predetermined level. For example, if the valve device is closed, the piston is held in locking position by the hydraulic fluid sealed in the forward moiety of the rearward chamber. However, an increase in temperature causes the hydraulic fluid contained in the forward moiety of the rearward chamber to expand in the forward moiety of the rearward chamber, thereby increasing the pressure in the forward moiety of the rearward chamber. Accordingly, the pressure relief valve is used to release hydraulic fluid into the forward chamber to avoid excessive hydraulic pressure in the forward moiety of the rearward chamber. The pressure relief valve can be located in the intermediate wall.
Alternatively, the thermal expansion of the hydraulic fluid can be compensated for by expanding the forward moiety of the rearward chamber without moving the piston. In this embodiment, the intermediate wall slides to allow the forward moiety of the rearward chamber to expand with the thermal expansion of the hydraulic fluid. In this embodiment, the hydraulic actuator includes an intermediate wall seal and an intermediate restrainer. The intermediate wall has a cross-sectional shape corresponding to that of the actuator enclosure, is sized and dimensioned to closely conform to the interior surface of the actuator enclosure, and is slidably disposed in the actuator enclosure. The intermediate wall seal is used for slidably sealing the intermediate wall to the interior surface and prevents the flow of hydraulic fluid between the intermediate wall and the interior surface.
The intermediate restrainer is used for restricting the sliding of the intermediate wall in the actuator enclosure. The intermediate restrainer restricts the sliding of the intermediate wall and allows the intermediate wall to move only the distance necessary to compensate for the thermal expansion. For example, the intermediate restrainer can be at least one intermediate spring which inhibits the sliding of the intermediate wall. In this embodiment, if the fluid in the forward moiety of the rearward chamber expands, due to a thermal expansion, the intermediate wall slides against the intermediate spring and provides room for the hydraulic fluid in the forward moiety of the rearward chamber to expand without the piston moving.
The fluid passageway connecting the forward chamber and the forward moiety of the rearward chamber in fluid communication can be a cavity disposed in the piston shaft. This cavity can have a forward and rearward passageway extending axially through the piston rod. The forward passageway is positioned so as to always be in fluid communication with the forward chamber and the rearward passageway is positioned so as to always be in fluid communication with the forward moiety of the rearward chamber. In this embodiment, for example, if the pressure of the hydraulic fluid in the forward chamber is greater than the pressure in the forward moiety of the rearward chamber, the hydraulic fluid can flow from the forward chamber into the forward passageway, through the cavity and rearward passageway and into the forward moiety of the rearward chamber. Alternatively, if the hydraulic fluid pressure is greater in the forward moiety of the rearward chamber, the hydraulic fluid can flow from the forward moiety of the rearward chamber into the rearward passageway, through the cavity and forward passageway, and into the forward chamber.
The cavity can have a narrow portion positioned between the forward and rearward passageways and a stem aperture extending through the piston. In this embodiment, the valve device can be a plug disposed in the cavity, having a stem end and an opposed stopper end. The stem end has a cross-sectional shape corresponding to that of the stem aperture, is sized and dimensioned to closely conform to that of the stem aperture, and is slidably disposed in the stem aperture with the stem end extending into the back variable chamber while the opposed stopper end is slidably disposed in the cavity.
The stopper end has a cross-sectional shape corresponding to the cross-sectional shape of the narrow portion of the cavity and the stopper end is sized and dimensioned to snugly fit into the narrow portion to block the flow of hydraulic fluid when the stopper end is inserted into the narrow portion. The plug is sized so that, when the stem end (which extends into the rear cavity) is pushed forward, the stopper end is inserted into the narrow portion of the cavity. The valve device is closed when the stopper end is inserted and pressed into the narrow valve seat portion of the cavity. In this embodiment, a stem seal is used to provide a sliding seal between the stem end of the plug and the stem aperture and a plug spring is disposed in the cavity between the stopper end of the plug and the forward passageway of the cavity. The stem seal inhibits the flow of hydraulic fluid between the stem end and the stem aperture and prevents the flow of hydraulic fluid between the cavity and the rearward chamber. The plug spring is of sufficient resiliency to move the stopper end of a plug out of the narrow portion of the cavity when the forward pushing force on the stem is not present.
Preferably, the cavity has a circular cross section and the plug has the shape of a right circular cylinder. This embodiment is preferred due to manufacturing considerations and seal design considerations.
The hydraulic actuator can further include a spring-loaded locking ram which provides a forward pushing force on the valve stem when the valve stem makes contact with the locking ram as the piston is retracted to its locking position. The locking ram loading spring provides a sufficiently higher valve stem forward closing force then the opposing opening force of the plug spring. When the valve stem is pushed totally forward by the locking ram, the stopper end of the sealing surface of the plug mates with the passageway cavity valve seat and closes the valve. In this embodiment, the locking ram is positioned between the rearward end wall and the piston. The locking ram has a cross-sectional shape corresponding to that of the actuator enclosure, is sized and dimensioned to closely conform to the interior surface of the actuator enclosure, and is slidably disposed in the actuator enclosure.
The locking ram seal slidably seals the locking ram to the interior surface and prevents the flow of hydraulic fluid between the locking ram and the interior surface. The locking ram is position restrained by a mechanical stop against its forward surface such that a preload is maintained on the locking ram loading spring.
The locking ram spring is a spring which is stiffer than the plug spring, and is disposed between the locking ram and the rearward end wall, such that it inhibits the rearward motion of the locking ram when the plug stem makes contact with the locking ram. The cavity housing the locking ram spring can be unpressurized.
In this embodiment, when the stem contacts the locking ram, the stopper end of the plug is inserted into the narrow portion of the cavity, thereby closing the fluid passageway since the locking ram spring is stiffer than the stem spring. If sufficient hydraulic fluid pressure is supplied into the rearward moiety, the locking ram moves towards the rearward end wall, since the piston is locked into position with the valve device being closed. Upon sufficient movement of the locking ram, the stem end of the plug no longer contacts the locking ram, and the stopper end of the plug is forced out of the narrow portion of the cavity by the stem spring. Accordingly, the fluid passageway is opened and the hydraulic actuator is unlocked.
The invention provides a relatively simple way to lock a hydraulic actuator in a predetermined position. The invention is structurally simple, easy and relatively inexpensive to manufacture and provides reliable locking of a hydraulic actuator without the need for complicated moving parts. Since the locking force is provided by a trapped fixed volume of fluid being compressed by external forces acting on the piston rod, the locking force is uniformly distributed within the actuator. Localized high shear stresses induced by mechanical wedge-type locking devices are eliminated.
DRAWINGS
These and other features, aspects and advantages of the present invention will become better understood with reference to the following description, appended claims and accompanying drawings where:
FIG. 1 is a side, cutaway view of a locking hydraulic actuator embodying features of the present invention, the actuator having a pressure relief valve positioned in a stationary intermediate wall;
FIG. 2 is a side, cutaway view of a second locking hydraulic actuator embodying features of the present invention with the hydraulic actuator extending, the actuator having no pressure relief valve but, instead, having a forward-only slidable intermediate wall restrained by a stiff resilient element such as a Bellville Spring;
FIG. 3 is a side, cutaway view of the locking hydraulic actuator of FIG. 2 showing the hydraulic actuator locked in a predetermined location; and
FIG. 4 is a side, cutaway view of the locking hydraulic actuator of FIG. 2 showing the hydraulic actuator in mid-stroke.
DESCRIPTION
The following discussion describes in detail one embodiment of the invention and several variations on that embodiment. This discussion should not be construed as limiting the invention to that particular embodiment or to those particular variations. Practitioners skilled in the art will recognize numerous other embodiments and variations as well. For the definition of the complete scope of the invention, the reader is directed to the appended claims.
The word "cylinder" as used in the application means the surface traced by a straight line moving parallel to a fixed straight line and intersecting a fixed curve.
The present invention is a method for locking a hydraulic actuator in a predetermined position and a locking hydraulic actuator 10 useful in the practice of the method. Referring to the drawings, a locking hydraulic actuator 10 according to the present invention comprises: (a) a housing member 12, (b) a piston 14, (c) a piston seal 16, (d) a piston rod 18, (e) an intermediate piston rod seal 20, (f) a forward piston rod seal 22, (g) a first port 24, (h) a second port 26, (i) a fluid passageway 28, and (j) a valve device 30.
The housing member 12 consists of a hollow cylinder 31 bounded by a forward end wall 32 and a rearward end wall 34. The forward end wall 32 and the rearward end wall 34 each cooperate to define an actuator enclosure 36 having an interior surface 38. An intermediate wall 40 is disposed within the actuator enclosure 36 between the forward end wall 32 and the rearward end wall 34. The forward end wall 32 and the intermediate wall 40 each have a central aperture 42 and 44, respectively. The intermediate wall 40 divides the actuator enclosure 36 into a forward chamber 46 and a rearward chamber 48. The rearward chamber 48 is separated by the piston 14 into a forward moiety 50 and a rearward moiety 52.
The central aperture 42 allows the piston rod to extend through the forward end wall 32. Typically, the aperture 42 in the forward end wall 32 has a circular cross-section to facilitate manufacturing and seal compatibility.
The forward end wall 32 and the rearward end wall 34 can be attached to the hollow cylinder 31 by a number of various methods. For example, the opposed ends of the hollow cylinder 31 can have female threads, and each wall can have corresponding male threads inserted into the respective ends of the hollow cylinder 31. Alternatively, the opposed ends of the hollow cylinder 31 can be welded to the respective ends of the hollow cylinder 31. Moreover, either the rearward end wall 34 or the forward end wall 32 can be manufactured as part of the housing member 12. As shown in the drawings, if the forward end wall 32 is attached by threads, a forward end wall seal 54, i.e., an O-ring or other type of seal, must be used to seal the interface between the forward end wall 32 and the hollow cylinder 31.
As shown in the drawing, a rearward actuator attachment element 56 can be attached to the rearward end wall 34. The rearward actuator attachment element 56 provides a linking hole 58 which allows the hydraulic actuator 10 to be attached to a stationary structural element. The rearward actuator attachment element 56 can be welded, threaded, or machined as part of the rearward end wall 34.
The size and dimensions of the housing member 12 can vary according to the task that is required from the hydraulic actuator 10 and the source of pressurized hydraulic fluid. For example, the hydraulic actuator 10 becomes more powerful as the cross-sectional piston cylinder area of the actuator enclosure 36 increases and/or the hydraulic pressure increases. Methods for the sizing of hydraulic actuators 10 is well known by those skilled in the art.
The central aperture 44 allows the piston rod 18 to extend through the intermediate wall 40. Like the aperture 42 in the forward end wall 32, the aperture 44 in the intermediate wall 40 preferably has a circular cross-section to facilitate manufacturing and seal compatibility.
The cross-section of the actuator enclosure 36 can be any shape. However, in most instances, a circular cross-section is the common shape in the industry and is preferred due to manufacturing considerations and seal compatibility. Additionally, the interior surface 38 of the housing member 12 should have a fine finish to provide a good interface for all dynamic seals (i.e., the piston seal 16, the intermediate wall seal 66 and the locking ram seal 112) which slide against the interior surface 38.
The hydraulic actuator 10 can include a relief valve 60 for releasing hydraulic fluid from the forward moiety 50 of the rearward chamber 48 into the forward chamber 46 when the pressure of the hydraulic fluid in the forward moiety 50 of the rearward chamber 48 reaches a predetermined high level. The pressure relief valve 60 prevents the overpressuring of the forward moiety 50 of the rearward chamber 48 from thermal expansion of hydraulic fluid during the periods of time when fluid in the forward moiety of the rearward chamber is trapped therein. The pressure relief valve 60 can be any device capable of releasing the hydraulic fluid from the forward moiety 50 of the rearward chamber 48 into the forward chamber 46 when the pressure of the hydraulic fluid in the forward moiety 50 of the rearward chamber 48 reaches a predetermined limit. The size of the relief valve 60 will vary dependent upon the size and the particular use of the hydraulic actuator 10.
As shown in FIG. 1, this pressure relief valve 60 can be located in the intermediate wall 40. In this embodiment, the relief valve 60 is threaded into an opening in the intermediate wall 40. Thus, when pressure in the forward moiety 50 of the rearward chamber 48 reaches excessive levels, the relief valve 60 opens to allow for the flow of hydraulic fluid through the relief valve 60 into the forward chamber 46 until the pressure in the forward moiety 50 of the rearward chamber 48 falls to allowable levels.
The intermediate wall 40 is rigidly attached to the actuator enclosure 36 in the embodiment in which a relief valve 60 is utilized. An intermediate wall seal 64, i.e., O-ring or other type of seal, can be used to seal between the intermediate wall 40 and the interior surface 38 where necessary.
Instead of employing a relief valve 60 to relieve excess hydraulic pressure created by thermal expansion within the forward moiety 50 of the rearward chamber 48, the intermediate wall 40 can be slidably disposed in the actuator enclosure 36 with an intermediate wall seal 66 and an intermediate restrainer 68. This embodiment is illustrated in FIGS. 2-4. In this embodiment, the intermediate wall 40 has a cross-sectional shape corresponding to that of the actuator enclosure 36, and the intermediate wall 40 is shaped and dimensioned to closely conform to the interior surface 38 of the actuator enclosure 36. For example, if the interior surface 38 has a circular cross-section, the intermediate wall 40 will have the shape of a right circular cylinder. Typically, this shape is preferred due to manufacturing concerns and seal compatibility.
The intermediate wall seal 66 prevents the flow of hydraulic fluid between the intermediate wall 40 and the interior surface 38. The intermediate wall seal 66 can be any seal capable of slidably sealing the intermediate wall to the interior surface 38 of the actuator enclosure 36. Typically, the intermediate wall seal 66 is an O-ring type seal commonly known by those skilled in the art. The design of the intermediate wall seal 66 depends upon the shape of the interior surface 38. The intermediate wall seal 66 can be made of a rubber material. However, the type of material used may vary according to the hydraulic fluid used and/or to the work environment.
The intermediate restrainer 68 can be any device capable of restricting the sliding of the intermediate wall 40 in the actuator enclosure. The intermediate restrainer 68 restricts the sliding of the intermediate wall 40 but, under certain conditions, allows for thermal expansion of the hydraulic fluid contained in the forward moiety 50 of the rearward chamber 48 by allowing the size of the forward moiety 50 of the rearward chamber 48 to expand. As shown in FIGS. 2-4, the intermediate restrainer 68 can comprise at least one intermediate spring.
The intermediate restrainer 68 can be any type of spring or springs that, when disposed between the intermediate wall 40 and the forward end wall 32, inhibits the sliding of the intermediate wall 40 and does not interfere with the sliding of the piston rod 18. The stiffness of the intermediate restrainer 68 will vary according to the size of the hydraulic actuator 10 and design considerations. As shown in FIGS. 2-4, the intermediate restrainer 68 can be two opposed Bellville springs positioned between the intermediate wall 40 and the forward end wall 32. Alternatively, the intermediate restrainer 68 can be a coil spring sized to fit into the forward chamber 46.
The piston 14 has a cross-sectional shape which corresponds to that of the actuator enclosure 36. The piston 14 is shaped and dimensioned to closely conform to the interior surface 38 of the actuator enclosure 36 so as to be slidably disposed within the actuator enclosure 36. The size and the shape of the piston 14 and the actuator enclosure 36 will vary according to the task to be performed. The potential load-carrying capability of the hydraulic actuator 10 increases as the cross-sectional area of the piston 14 increases. The piston 14 has a forward facing surface 72 and a rearward facing surface 74.
The piston seal 16 can be any seal which slidably seals the piston 14 to the interior surface 38 of the actuator enclosure 36. In most instances, the piston seal 16 is an O-ring type seal commonly known by those skilled in the art. Alternatively, the piston seal 16 can be any other type of seal. The design of the piston seal 16 depends upon the shape of the interior surface 38 and the piston 14. Typically, the piston seal 16 is made of a rubber material. However, the type of material used will vary according to the type of material which will not be adversely affected by the hydraulic fluid or the work environment.
The piston rod 18 has a first end 76 which is attached to the forward facing surface 72 of the piston 14 and an opposed second end 78 which extends away from the housing member 12. The piston rod 18 is attached to the piston 14 and moves with the piston 14. The piston rod 18 extends through the central apertures 42 and 44 in the intermediate wall 40 and forward end wall 32, respectively. The piston rod 18 can be any size or shape which corresponds to the central apertures 42 and 44, respectively, in the intermediate wall 40 and the forward end wall 32. Preferably the piston rod 18 is a right circular cylinder because of ease of manufacture and compatibility with seals. Additionally, this shape is preferred since it provides maximum strength for the cross-sectional area.
The first end 76 of the piston rod 18 is interference fitted into an opening in the piston 14. Alternatively, the first end 76 of the piston rod 18 can be attached to the piston 14 by welds or alternatively by threading the piston rod 18 into the piston 14. Referring to the embodiments shown in the drawings, a front forward piston rod attachment element 82 is attached to the second end 78 of the piston rod 18. The forward piston rod attachment element 82 provides an opening 84 to attach the piston rod 18 of the hydraulic actuator 10 to the object or device which is to be moved or held by the hydraulic actuator 10. As shown in the figures, the second end 78 of the piston rod 18 can have female threads and the forward piston rod attachment element 82 can have corresponding male threads. Alternatively, the forward piston rod attachment element 82 can be attached to the second end 78 of the piston rod 18 by welds or be machined as part of the piston rod 18.
The intermediate piston rod seal 20 can be any seal capable of slidably sealing the piston rod 18 to the aperture 44 in the intermediate wall 40. Similarly, the forward piston rod seal 22 can be any device capable of slidably sealing the piston rod 18 to the aperture 42 in the forward end wall 32. The type of seal utilized will depend upon the size and shape of the intermediate wall aperture 44, the forward end wall aperture 42, and the cross-sectional size and shape of the piston rod 18. In most instances, the intermediate wall aperture 44 and forward end wall aperture 42 have a circular cross-section, and the piston rod 18 has the shape of a right circular cylinder. In this embodiment, the intermediate piston rod seal 44 and the forward piston rod seal 42 will typically be an O-ring type seal commonly known by those skilled in the art. The design of the seals will depend upon the shape of the interior surface 38. Typically, these seals are made of a rubber materials. However, the type of material used for the seal will vary according to the type of material which will not be adversely affected by the hydraulic fluid or the work environment.
The first port 24 allows the hydraulic fluid to flow from a source of pressurized hydraulic fluid into the forward chamber 46 of the hydraulic actuator 10, or conversely for fluid to flow from the forward chamber to an external return sump. The size and shape of the first port 24 can vary and will depend upon the size and shape of the connecting tubes or pipes which are used to connect the source of pressurized hydraulic fluid to the hydraulic actuator 10. As shown in the drawings, the first port 24 comprises an opening extending from the exterior of the housing member 12 into the forward chamber 46 near the forward end wall 32. The first port 24 can have female pipe threads or other types of threads to connect the external source or return sump to the forward chamber 46. In embodiments where the intermediate wall 40 can slide towards the forward end wall 32, the first port 24 must be located so that the movement of the intermediate wall 40 does not affect the flow of hydraulic fluid between the first port 24 and the forward chamber 46.
Similarly, the second port 26 allows the hydraulic fluid to flow into or out of the rearward moiety 52 of the hydraulic actuator 10. The size and shape of the second port 26 can vary and will depend upon the size and shape of the connecting tubes or pipes which are used to connect the source of pressurized hydraulic fluid to the hydraulic actuator 10. As shown in the drawings, the second port 26 comprises an opening extending from the exterior of the housing member 12 into the rearward moiety 52 near locking ram 90 (described below). The second port 26 can have female pipe threads or other types of threads to connect the source of pressurized hydraulic fluid to the rearward moiety 52. In embodiments where a locking ram 90 slides in the actuator enclosure 36, the second port 26 must be located so that the movement of the locking ram 90 does not affect the flow of hydraulic fluid between the second port 26 and the rearward moiety 52.
The fluid passageway 28 can be any passageway which connects the forward chamber 46 and the forward moiety 50 of the rearward chamber 48 in fluid communication. Basically, the fluid passageway 28 allows for the flow of hydraulic fluid between the forward chamber 46 and the forward moiety 50 of the rearward chamber 48. For example, hydraulic fluid will flow from the forward chamber 46 through the fluid passageway 28 into the forward moiety 50 of the rearward chamber 48 if the pressure in the forward chamber 46 is greater than the pressure in the forward moiety 50 of the rearward chamber 48. Alternatively, hydraulic fluid will flow from the forward moiety 50 of the rearward chamber 48 through the fluid passageway 28 into the forward chamber 46 if the pressure in the forward moiety 50 of the rearward chamber 48 is greater than the pressure in the forward chamber 46.
In the embodiment shown in the figures, the fluid passageway 28 is a cavity disposed in the piston rod 18, the passageway 28 having a forward passageway 94 and a rearward passageway 96 extending laterally from the cavity 92 through the piston rod 18. The size of the passageway 28 will vary according to the size of the cross-section of the piston rod 18 and the type of hydraulic fluid utilized. Preferably, the cavity passageway 28 is positioned on the central axis of the piston rod 18 to reduce the effect that the passageway 28 will have on the strength of the piston rod 18. Preferably, the passageway 28 has a circular cross-sectional shape to facilitate manufacturing and seal compatibility.
The forward passageway 94 is positioned so that it will always be in fluid communication with the forward chamber 46 regardless of the position of the piston rod 18 and the intermediate wall 40. Typically, the forward passageway 94 is a hole which extends radially through the piston rod 18. The rearward passageway 96 is positioned so that it will always be in fluid communication with the forward moiety 50 of the rearward chamber 48 regardless of the position of the piston rod 18 and the intermediate wall 40. Similarly, the rearward passageway 96 is a hole which extends through the piston rod 18. The positioning of the forward and rearward passageways 94 and 96 will depend upon the size and shape of the hydraulic actuator 10. The size of the forward and rearward passageways 94 and 96 can vary according to the size of the piston rod 18 and the type of hydraulic fluid utilized.
The passageway 28 can further comprise a narrow valve seat portion 98 positioned between the forward and rearward passageways 94 and 96 and a stem aperture 100 extending through the piston 14.
The valve device 30 can be any device capable of alternately opening and closing the passageway 28. As shown in the drawings, the valve device 30 can comprise a plug 102 having a stem end 104, an opposed stopper end 106, a stem seal 108 and a plug spring 110. The stem end 104 of the plug 102 is slidably disposed in the stem aperture 100 and extends into the rearward moiety 52 of the rearward chamber 48. The stem end 104 has a cross-sectional shape corresponding to that of the stem aperture 100, with the stem end 104 being sized and dimensioned to closely conform to that of the stem aperture 100. The opposed stopper end 106 of the plug has a conical cross-section shape corresponding to the narrow circular portion 98 of the passageway 28. The stopper end 106 is sized and dimensioned to snugly close the narrow annular portion 98 to prevent the flow of hydraulic fluid when the stopper end 106 is inserted into the narrow annular portion 98 of the passageway 28.
The valve device 30 is in the closed position when the stopper end 106 of the plug 102 is snugly mated into the narrow portion 98 of the passageway 28. Alternatively, the valve device 30 is in the open position when the stopper end 106 is not inserted into the narrow annular portion 98 of the passageway 28. The plug 102 is sized so that the stopper end 106 is inserted into the narrow valve seat portion 98 of the passageway 28 when the stem end 104 contacts the locking ram 90.
The size and shape of the plug 102 can vary according to the size and shape of the passageway 28. Preferably, the passageway 28 has a circular cross-sectional shape, and the plug 102 is the shape of a circular cylinder to facilitate manufacturing and seal compatibility.
The stem seal 108 is used for slidably sealing the stem end 104 of the plug to the stem aperture 100. The stem seal 108 is being used to prevent the flow of hydraulic fluid between the passageway 28 into the rearward moiety 52 of the rearward chamber 48. Typically the stem seal 108 is an O-ring type seal commonly known by those skilled in the art. The design of the stem seal 108 depends upon the shape of the stem aperture 100. Typically, the stem seal 108 is made of a rubber materials. However, the type of material used will vary according to the type of material which will not be adversely affected by the hydraulic fluid or the work environment.
The plug spring 110 can be disposed in the cavity between the stopper end 106 of the plug 102 and the forward passageway 94 of the passageway 28. The plug spring 110 can be a coil spring or any type of spring which is of sufficient strength to move the stopper end 106 of the plug 102 away from the narrow valve seat portion 98 of the cavity 92 when the stem end 104 of the plug 102 is not in contact with the locking ram 90. In embodiments with a locking ram 90, the plug spring 110 cannot be as stiff as the locking ram spring 114 (described below) so that when the stem end 104 contacts the locking ram 90, the plug 102 moves instead of the locking ram 90.
The source of pressurized hydraulic fluid (not shown) can be any source which supplies sufficient volume and pressure of hydraulic fluid to the hydraulic actuator as is required by the particular task that needs to be accomplished by the hydraulic actuator. Accordingly, the source of pressurized hydraulic fluid will vary according to the task that needs to be performed.
The type of hydraulic fluid utilized will also vary according to the task to be performed. In most instances, the hydraulic fluid is a hydraulic oil or other type of oil since this type of hydraulic fluid inhibits corrosion of the hydraulic actuator and reduces friction between the moving parts, thereby extending the life of the hydraulic actuator. Alternately, the hydraulic fluid could be any fluid, such as water which is substantially incompressible.
A locking ram 90 can be slidably disposed in the actuator enclosure 36 between the piston 14 and the rearward end wall 34 with a locking ram seal 112 and a locking ram spring 114. In this embodiment, the locking ram 90 has a cross-sectional shape corresponding to that of the actuator enclosure 36, and the locking ram 90 is shaped and dimensioned to closely conform to the interior surface of the actuator enclosure 36. For example, if the interior surface 38 has a circular cross-section, the locking ram 90 will have the shape of a right circular cylinder. Typically, this shape is preferred due to ease of manufacturing and seal compatibility.
The plug 102 is inserted into the narrow portion 108 of the cavity 92 when the stem end 104 contacts the locking ram 90. When the hydraulic actuator 10 is locked, the locking ram 90 provides space for the rearward moiety 52 of the rearward chamber 48 to expand to release the stem end 104 of the plug 102. For example, if sufficient hydraulic forced rearward applied to the rearward moiety 52 of the rearward chamber 48 when the hydraulic actuator 10 is locked, the locking ram 90 forced rearward from the piston 14 allowing the plug spring 110 to push the plug 102 out of the narrow valve seat portion 98 of the passageway 28 and thus unlock the actuator.
The locking ram seal 112 can be any seal capable of slidably sealing the locking ram to the interior surface 38 of the housing member 12. The locking ram seal 112 prevents the flow of hydraulic fluid between the locking ram 90 and the interior surface 38. Typically, the locking ram seal 112 is an O-ring type seal commonly known by those skilled in the art. Alternatively, the seal 112 can be any other type of seal. The design of the seal 112 depends upon the shape of the interior surface 38. Typically, the locking ram seal 112 is made of a rubber material; however, the type of material used will vary according to the type of material which will not be adversely affected by the hydraulic fluid or the work environment.
The locking ram spring 114 can be any device capable of restricting rearward motion of the locking ram 90 in the actuator enclosure 36. The spring restrainer 114 restricts the sliding motion of the locking ram 90 until sufficient hydraulic pressure is supplied in the rearward moiety 52 of the rearward chamber 48. The forward motion of the locking ram 90 may be limited by a mechanical stop 118 which provides a preload to the locking ram spring 114. The rearward motion of the locking ram 90 is limited by the internal protrusion of the rearward end wall 34.
The mechanical stop 118 can be provided by the interior surface 38 of the actuator enclosure 36, having a reduced cross-sectional diameter at a predetermined locking ram stop position. Thus, the locking ram 90 cannot slide past the mechanical stop 118. Alternatively, as shown in FIGS. 2-4, the mechanical stop 118 can be an annular groove disposed on the interior surface 38 of the actuator enclosure 36 with a snap-ring positioned in the annular groove providing the stop 118 at the predetermined limit.
The locking ram spring 114 can be any type of spring or springs that, when disposed between the locking ram 90 and the rearward end wall 34, inhibits the sliding of the locking ram 90. The stiffness of the spring 114 will vary according to the size of the hydraulic actuator 10 and will depend upon design considerations of when the locking ram 90 needs to move to allow for the plug to move to unlock the actuator. The stiffness of the spring 114 and the cross-sectional area of the locking ram 90 determines the hydraulic pressure level required in the rearward moiety 52 of the rearward chamber 48 to move the locking ram 90. The rearward end wall 34 may have a breather opening 126 to maintain atmospheric pressure on the rear surface of the locking ram 90.
In operation, hydraulic fluid is supplied to the first port 24 to move the hydraulic actuator 10 into the predetermined locking position. The hydraulic fluid, which is supplied to the first port 24, flows into the forward chamber 46 of the hydraulic actuator 10 through the fluid passageway 28 into the forward moiety 50 of the rearward chamber 48. If sufficient hydraulic fluid flows into the forward moiety 50 of the rearward chamber 48 and a sufficient pressure is reached, the piston 14 begins to move towards the rearward end wall 34. The hydraulic fluid in the forward moiety 50 of the rearward chamber 48 causes the piston 14 and the accompanying piston rod 18 to retract. When the piston 14 moves to the predetermined locking position, the valve device 30 is closed, sealing the forward moiety 50 of the rearward chamber 48.
The valve device 30 closes when the plug 102 is inserted into the narrow valve seat portion 98 of the passageway 28. When hydraulic fluid is supplied to the first port 24, the hydraulic fluid flows from the forward chamber 46, through the forward passageway 94, through the passageway 28, and out the rearward passageway 96 into the forward moiety 50 of the rearward chamber 48. This hydraulic fluid then forces the piston 14 towards the rearward end wall 34, causing the piston 14 and piston rod 18 to move towards the rearward end wall 34. When the piston 14 moves a sufficient distance, the stem end 104 of the plug 102 contacts the locking ram 90 and causes the stopper end 106 of the plug 102 to be inserted into the narrow valve seat portion 98 of the passageway 28, thereby closing the fluid passageway 28. The hydraulic fluid that is sealed in the forward moiety 50 of the rearward chamber 48 holds the piston 14 and the piston rod 18 at this locked position. If the temperature of the hydraulic fluid increases, excessive hydraulic pressure created by the thermal expansion of the hydraulic fluid is relieved by the relief valve 60 or the intermediate wall 40 moving against the intermediate spring 70 to expand the forward moiety 50 of the rearward chamber 48.
To unlock a locked actuator 10, the locking ram 90 is forced to move rearward towards the rearward wall 34 when sufficient hydraulic pressure is supplied to the rearward moiety of the rearward chamber 48. In this embodiment, once the locking ram 90 moves a prescribed distance, the stem end 104 of the plug 102 no longer contacts the locking ram 90, and the plug spring 110 causes the plug 102 to move out of the narrow valve seat portion 98 of the passageway 38, thereby opening the fluid passageway 28 for hydraulic fluid to flow between the forward moiety 50 of the rearward chamber 48 and the forward chamber 46 and, thereby, unlocking hydraulic actuator 10. Accordingly, the piston 14 moves towards the forward end wall 32, causing hydraulic fluid to flow from the forward moiety 50 of the rearward chamber 48 into the forward chamber 46 and out port 24.
The present invention provides a relatively simple way to lock the piston 14 and piston rod 18 of a hydraulic actuator 10 in a predetermined position. The structure of the locking hydraulic actuator 10 is relatively simple, thus making the hydraulic actuator 10 relatively easy and inexpensive to manufacture. Moreover, hydraulic pressure is used to lock the piston 10 in the predetermined position instead of locking members. Thus, the present invention provides uniformly distributed stresses induced by external unlock induced loads and is not subject to premature wear of the locking members, caused by localized high shear stresses in current typical wedge type locking mechanizations.
EXAMPLE
An example locking hydraulic actuator 10 has a circular cross-section with an internal diameter of 1.5 inches. The locking ram 90 has a surface area of 1.76 square inches. The diameter of the plug stem and 114 is 0.125 inches. The minimum annular clearance between the valve plug 102 and the valve seat 98 is 0.06 inches. The piston rod 18 has four radial holes, spaced apart at 90 degree intervals. Each radial hole has a diameter of about 0.09 inches. The piston rod 18 has a diameter of 0.72 inches. The lateral stroke distance of the piston rod 18 is 1.625 inches. The locking ram spring 114 has a free height of 1.5 inches, an installed height of 1.0 inches and exerts 150 pounds of preload force. The plug spring 110 has a free length of 1.0 inches, an installed length of 0.75 inches and exerts 28 pounds of preload force. The intermediate restrainer 68 are a pair of Bellville springs preloaded for a forced loading on the intermediate wall of greater than 2,600 pounds. The diameter of the piston is 1.5 inches.
This example hydraulic actuator 10 is designed to use a system operating pressure of 1,500 psig with a return line pressure of 25 psig. The operating temperature range of the example actuator is -65° to +165° F. The maximum extension load is 2600 pounds of force. The maximum retraction load is 2,000 pounds of force. The locking mechanism of the hydraulic actuator 10 is designed to hold 1,200 pounds of force tension load, and it is designed to release against about 1,200-pound tension load when the inlet port pressure is between about 75 and 100 psig.
Although the present invention has been described in considerable detail with reference to certain preferred versions, many other versions should be apparent to those skilled in the art. Therefore, the spirit and scope of the appending claims should not necessarily be limited to the description of the preferred versions contained herein. | A method for locking a hydraulic actuator in a predetermined position and a locking hydraulic actuator are provided. The method includes the steps of supplying hydraulic fluid to a forward chamber in the hydraulic actuator, transferring the hydraulic fluid from the forward chamber into a forward moiety of the rearward chamber in the hydraulic actuator, and sealing the hydraulic fluid in the forward moiety of the rearward chamber to accomplish the locking function. Conversely, the actuator lock is released by the application of fluid supply pressure to the rearward variable chamber. | 5 |
FIELD OF THE INVENTION
This invention relates software programs known in the art as routers. That is, a program that determines the signal and power paths among elements of a large scale integrated circuit. More particularly, the invention relates to a novel method to organize the tie net data presented to the router program in order to improve router performance.
BACKGROUND OF THE INVENTION
As will be appreciated by those skilled in the art, a large-scale integrated circuit design is often used over and over again to implement different functional designs. This repeated use results in a large number (often thousands) of elements in the integrated circuit design that are not used for a specific functional design. These elements unused in a particular design are connected directly to a power signal, logical “1” or logical “0” and are referred to as being tied up (connected to logical one/vdd) or tied down (connected to logical 0/gnd).
In the prior art, unedited tie net data is used by the router to route the connections of an unused element to the power grid. This unedited tie net data lumps unused elements in single large tie net. Although these connections are not timing critical, and thus the respective routing paths for these connections is not critical, routing programs have difficulty in routing the tie net data as presented to the router in the prior art due to the massively parallel nature of the problem seen by the router in routing the tie net. A routing problem that is massively parallel can cause the router to come up with sub-optimal solutions and take a long time to complete.
SUMMARY OF THE INVENTION
An object of this invention is the provision of method of modeling the tie nets that preprocesses the design and edits the resulting net list so that the tie connections no longer appear to the router as a massively parallel problem and thus can be more simply and efficiently routed.
Briefly, this invention contemplates the provision of a method for preprocessing tie net routing data in which the preprocessing method organizes the data into a plurality of tie nets each based on an optimal connection path between a pin or set of pins and the power grid. The router then routs the data embodying the thusly-simplified plurality of tie nets. Once the routing is complete, post processor takes the routed design and returns it to its original net list state while keeping the routing solution.
BRIEF DESCRIPTION OF THE DRAWINGS
The subject matter, which is regarded as the invention, is particularly pointed out and distinctly claimed in the claims at the conclusion of the specification. The foregoing and other objects, features, and advantages of the invention are apparent from the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 is a block diagram that defines graphically some of the terms used in this application
FIG. 2 is a flow chart of the pre-routing process to organize tie net data in accordance with the teachings of this invention.
DETAILED DESCRIPTION OF THE INVENTION
As will be appreciated by those skilled in the art, present day large scale integrated circuit designs commonly use previously existing designs as the base hardware design consisting of logical elements and a power grid. The elements of the previously existing design are logically connected to carry out the functions of the new design. The router program determines the paths for the physical connections to make the logical connections called for in the new design. As explained above, many of the logical elements in the previously existing design are often not used in the new design an these elements are connected to a logic “1’ or “0”.
Definitions
Cell—A cell contains the implementation of a part of the logic being used in the design. It has blockages that indicate to the design containing it where its shapes are so they can be avoided and contains terminals that represent the points on the cell at which logical connections can be made to the logic.
Instance—Each unique usage of a cell is an instance. Each instance has its own instance name and instance terminals that are this instance's connections to the terminal of the cell.
Net—A net defines the connections between instance terminals that implement the logic of the design being implemented.
Router—A program that creates physical connections for a net. Electrically connecting the instance terminals together.
Referring now to FIG. 2 , the pre routing process for tie net in accordance with the teachings of this invention starts by creating a tie overlay cell that encompasses the shapes that will be removed from the power grid and used in the tie net routing, block 20 . This overlay cell data is instantiated into the overall design data, block 21 . For each of the pins that that need to be tied the associated power net is identified in the design (i.e. vdd for a tieup), block 22 . The cells that contain the power grid wires for each identified net are identified and the power wires in that net are identified, block 24 . For each of the unused instance terminals the physical pin location for the pin is identified (block 26 ) and the closest power wire identified from block 24 is identified, block 28 . That closest power wire is moved (block 30 ) from the cell that contained it into the overlay cell created in block 20 . A unique net name is created to represent this tie connection. A net with this name is created in the overlay cell and the power wire is attached to this net, block 32 . Another net with this same name is created in the top design, block 34 . The top level cell is the design being working on, and contains the placed cell instances and nets that connect them. The overlay cell is instantiated in this design as a place holder for the power grid shapes that will be moved around during processing. The unused instance terminal is detached from the power net it was associated with and attached to this net created in block 34 , block 36 . The design data with the tie nets thusly simplified is then sent to the router program in order to route the connections, block 38 . Following routing the net list is returned to its original state, block 40 . This encompasses removing the overlay cell, replacing the power shapes from the overlay cell back into their original locations, deleting the unique tie nets that were created in block 34 , returning the unused instance terminals to the original power net they were connected to and moving the shapes the router created on the tie nets to this same original power net.
The capabilities of the present invention can be implemented in software.
As one example, one or more aspects of the present invention can be included in an article of manufacture (e.g., one or more computer program products) having, for instance, computer usable media. The media has embodied therein, for instance, computer readable program code means for providing and facilitating the capabilities of the present invention. The article of manufacture can be included as a part of a computer system or sold separately.
Additionally, at least one program storage device readable by a machine, tangibly embodying at least one program of instructions executable by the machine to perform the capabilities of the present invention can be provided.
The flow diagrams depicted herein are just examples. There may be many variations to these diagrams or the steps (or operations) described therein without departing from the spirit of the invention. For instance, the steps may be performed in a differing order, or steps may be added, deleted or modified. All of these variations are considered a part of the claimed invention.
While the preferred embodiment to the invention has been described, it will be understood that those skilled in the art, both now and in the future, may make various improvements and enhancements which fall within the scope of the claims which follow. These claims should be construed to maintain the proper protection for the invention first described. | A method for preprocessing tie net routing data organizes the data into a plurality of tie nets each based on an optimal connection path between a pin or set of pins and the power grid. The router then routs the data embodying the thusly-simplified plurality of tie nets. Once the routing is complete, post processor takes the routed design and returns it to its original net list state while keeping the routing solution. | 6 |
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